Substrate processing method, exposure apparatus, and method for producing device by immersing substrate in second liquid before immersion exposure through first liquid

ABSTRACT

A substrate processing method which includes an exposure step wherein an immersion area of a first liquid is formed on a substrate and the substrate is exposed by being irradiated with an exposure light through the first liquid, and an immersion step wherein the substrate is immersed in a second liquid before the exposure step. By this method, occurrences of problems caused by adhesion marks, which are always involved in immersion exposure, can be reduced.

TECHNICAL FIELD

The present invention relates to a substrate processing method includinga step for exposing a substrate, an exposure apparatus, and a method forproducing a device.

BACKGROUND ART

An exposure apparatus, which performs the projection exposure onto aphotosensitive substrate with a pattern formed on a mask, is used in thephotolithography step as one of the steps of producing microdevices suchas semiconductor devices and liquid crystal display devices. Theexposure apparatus includes a mask stage for supporting the mask and asubstrate stage for supporting the substrate. The pattern of the mask issubjected to the projection exposure onto the substrate via a projectionoptical system while successively moving the mask stage and thesubstrate stage. In the microdevice production, it is required torealize a fine and minute pattern to be formed on the substrate in orderto achieve a high density of the device. In order to respond to thisrequirement, it is demanded to realize a higher resolution of theexposure apparatus. A liquid immersion exposure apparatus, in which aliquid immersion area is formed by filling the space between theprojection optical system and the substrate with a liquid to perform theexposure process via the liquid of the liquid immersion area, has beencontrived as one of means to realize the high resolution, as disclosedin International Publication No. 99/49504.

DISCLOSURE OF THE INVENTION Task to be Solved by the Invention

When the liquid remains on the substrate, and the liquid is vaporized,then there is such a possibility that any adhesion trace (so-calledwater mark) may be formed on the substrate. The adhesion trace acts as aforeign matter. Therefore, if various processes including, for example,the development process are executed for the substrate in a state inwhich the adhesion trace is formed on the substrate, an inconveniencesuch as the pattern defect arises. If the substrate is unloaded in astate in which the adhesion trace is formed on the substrate, thefollowing inconvenience arises. That is, a transport (contaminated)therewith, and a carrier for accommodating the substrate is pollutedtherewith.

The present invention has been made taking the foregoing circumstancesinto consideration, an object of which is to provide a substrateprocessing method, an exposure apparatus, and a method for producing adevice based on the use of the exposure apparatus, wherein it ispossible to suppress the occurrence of any inconvenience which would beotherwise caused by the foreign matter (for example, the adhesion traceof the liquid) adhered onto a substrate.

Solution for the Task

In order to achieve the object as described above, the present inventionadopts the following constructions.

According to a first aspect of the present invention, there is provideda substrate processing method including an exposure step for exposing asubstrate by forming a liquid immersion area of a first liquid on thesubstrate and radiating an exposure light beam onto the substratethrough the first liquid; and an immersing step for immersing thesubstrate in a second liquid before the exposure step.

According to the first aspect of the present invention, the substrate isimmersed in the second liquid before radiating the exposure light beamonto the substrate through the first liquid (in the step before theexposure step). Accordingly, it is possible to suppress the occurrenceof the inconvenience which would be otherwise caused by an adhesiontrace formed on the substrate. The immersion of the substrate in thesecond liquid in the immersing step is the operation which is differentfrom the operation of contact of the substrate with the first liquid inorder to perform the liquid immersion exposure in the exposure step.

According to a second aspect of the present invention, there is provideda substrate processing method including an exposure step for exposing asubstrate by radiating an exposure light beam onto the substrate througha first liquid; and a cleaning step for cleaning the substrate with asecond liquid after the substrate has made contact with the first liquidin order to miniaturize or remove a foreign matter adhered onto thesubstrate due to an eluted matter eluted from the substrate into thefirst liquid.

According to the second aspect of the present invention, the substrateafter making the contact with the first liquid is cleaned with thesecond liquid. Accordingly, the foreign matter (for example, theadhesion trace of the liquid), which is adhered onto the substrate dueto the eluted matter eluted from the substrate into the first liquid,can be decreased or miniaturized to have minute sizes, or removed.Therefore, it is possible to suppress the occurrence of theinconvenience which would be otherwise caused by the foreign matter asdescribed above.

According to a third aspect of the present invention, there is provideda substrate processing method including holding a substrate by a holder;an exposure step for exposing the substrate by radiating an exposurelight beam onto the substrate through a first liquid; and a cleaningstep for cleaning the exposed substrate with a second liquid whileholding the exposed substrate by the holder. According to the thirdaspect of the present invention, the foreign matter, which is adheredonto the substrate, can be decreased or miniaturized or removed bycleaning, with the second liquid, the substrate after the substrate hasmade contact with the first liquid while retaining the substrate by thesubstrate holder. Therefore, it is possible to suppress the occurrenceof the inconvenience which would be otherwise caused by the foreignmatter as described above.

According to a fourth aspect of the present invention, there is provideda method for producing a device; including the substrate processingmethod as defined in the first aspect; a step for developing thesubstrate after the exposure step; and a step for processing thedeveloped substrate.

According to a fifth aspect of the present invention, there is provideda method for producing a device; including the substrate processingmethod as defined in the second or third aspect; a step for developingthe substrate; and a step for processing the developed substrate.

According to the methods for producing the device concerning the fourthand fifth aspects of the present invention, the substrate can beprocessed while suppressing the occurrence of the inconvenience whichwould be otherwise caused by the foreign matter (for example, theadhesion trace of the liquid). Therefore, it is possible to produce thedevice having the desired performance.

According to a sixth aspect of the present invention, there is providedan exposure apparatus which exposes a substrate by forming a liquidimmersion area of a first liquid on the substrate and radiating anexposure light beam onto the substrate through the first liquid; theexposure apparatus including a substrate holder which holds thesubstrate; and an immersion device which immerses the substrate in asecond liquid before exposing the substrate through the first liquid.

According to the sixth aspect of the present invention, the immersiondevice immerses the substrate in the second liquid before exposing thesubstrate by radiating the exposure light beam onto the substratethrough the first liquid. Accordingly, it is possible to suppress theoccurrence of the inconvenience which would be otherwise caused by theforeign matter (for example, the adhesion trace of the liquid) adheredonto the substrate.

According to a seventh aspect of the present invention, there isprovided an exposure apparatus which exposes a substrate by forming aliquid immersion area of a first liquid on the substrate and radiatingan exposure light beam onto the substrate through the first liquid; theexposure apparatus including a cleaning device which cleans thesubstrate with a second liquid after the substrate has made contact withthe first liquid in order to miniaturize or remove a foreign matteradhered onto the substrate due to an eluted matter eluted from thesubstrate into the first liquid.

According to the seventh aspect of the present invention, the cleaningdevice cleans, with the second liquid, the substrate after the substratehas made contact with the first liquid. Accordingly, it is possible todecrease or miniaturize or remove the foreign matter (for example, theadhesion trace of the liquid) adhered onto the substrate due to theeluted matter eluted from the substrate into the first liquid.Therefore, it is possible to suppress the occurrence of theinconvenience which would be otherwise caused by the foreign matter.

According to an eighth aspect of the present invention, there isprovided a method for producing a device, including using the exposureapparatus as defined in any one of the aspects described above.

According to the eighth aspect of the present invention, the substratecan be processed while suppressing the occurrence of the inconveniencewhich would be otherwise caused by the foreign matter (for example, theadhesion trace of the liquid) adhered to the substrate. Therefore, it ispossible to produce the device having the desired performance.

EFFECT OF THE INVENTION

According to the present invention, the predetermined process can besatisfactorily applied to the substrate, and it is possible to producethe device having the desired performance.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a device production system including an exposure apparatusaccording to a first embodiment.

FIG. 2 shows a schematic arrangement illustrating a main exposureapparatus body.

FIG. 3 shows a flow chart illustrating an example of the operation ofthe device production system.

FIG. 4 shows a side sectional view illustrating an example of asubstrate.

FIG. 5 shows an example of an immersion unit.

FIG. 6 schematically shows the behavior of the substrate for which theimmersion process is performed.

FIG. 7 shows an example of the operation for removing the liquid.

FIG. 8 shows an example of a temperature regulation mechanism.

FIG. 9 shows another example of the temperature regulation mechanism.

FIG. 10 shows a state in which the substrate held by a substrate holderis subjected to the liquid immersion exposure.

FIG. 11 schematically shows a state in which the exposure light beam isradiated onto the substrate.

FIG. 12 schematically shows the behavior of the substrate for which theheat treatment is performed.

FIG. 13 shows a flow chart illustrating an example of the operation of adevice production system according to a second embodiment.

FIG. 14 shows a plan view illustrating an example of the operation forcleaning the substrate.

FIG. 15 shows a side sectional view illustrating an example of theoperation for cleaning the substrate.

FIG. 16 shows an example of the operation for cleaning the substrateaccording to a third embodiment.

FIG. 17 shows a side sectional view illustrating an example of thesubstrate according to the third embodiment.

FIG. 18 schematically shows the behavior of the substrate for which theimmersion process is performed.

FIG. 19 shows a flow chart illustrating exemplary steps for producing amicrodevice.

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiments of the present invention will be explained below withreference to the drawings. However, the present invention is not limitedthereto.

First Embodiment

FIG. 1 shows an embodiment of a device production system provided withan exposure apparatus according to a first embodiment. With reference toFIG. 1, the device production system SYS includes an exposure apparatusEX-SYS, a coater/developer apparatus C/D-SYS, and a transport system Hwhich transports a substrate P. The exposure apparatus EX-SYS includesan interface IF which forms the connecting portion with respect to thecoater/developer apparatus C/D-SYS, a main exposure apparatus body EXwhich forms a liquid immersion area LR of a first liquid LQ1 on thesubstrate P and which exposes the substrate P by radiating the exposurelight beam EL onto the substrate P through the first liquid LQ1, and acontrol unit CONT which integrally controls the operation of the entireexposure apparatus EX-SYS. The coater/developer apparatus C/D-SYS isprovided with a main coater/developer body C/D including a coating unit(not shown) which coats the base material of the substrate P beforebeing subjected to the exposure process with a photosensitive material(resist), and a developing unit (not shown) which performs thedevelopment process for the substrate P after being subjected to theexposure process in the main exposure apparatus body EX. The mainexposure apparatus body EX is arranged in a first chamber apparatus CH1in which the cleanness is managed. On the other hand, the maincoater/developer body C/D, which includes the coating unit and thedeveloping unit, is arranged in a second chamber apparatus CH2 which isdistinct from the first chamber apparatus CH1. The first chamberapparatus CH1 for accommodating the main exposure apparatus body EX isconnected to the second chamber apparatus CH2 for accommodating the maincoater/developer body C/D via the interface IF.

The transport system H includes a first transport system H1 whichtransports the substrate P between the interface IF and the mainexposure apparatus body EX, and a second transport system H2 whichtransports the substrate P between the interface IF and maincoater/developer body C/D. The first transport system H1 constitutes apart of the exposure apparatus EX-SYS, and the second transport systemH2 constitutes a part of the coater/developer apparatus C/D-SYS. Thefirst transport system H1 is provided in the first chamber apparatusCH1, and the second transport system H2 is provided in the secondchamber apparatus CH2.

An immersion unit 30 for immersing the substrate P in a second liquidLQ2 and a temperature regulation mechanism 40 for regulating thetemperature of the substrate P are provided at intermediate positions ofthe transport passage of the transport system H. In this embodiment, theimmersion unit 30 and the temperature regulation mechanism 40 areprovided for the coater/developer apparatus C/D-SYS. The immersion unit30 and the temperature regulation mechanism 40 are provided atintermediate positions of the transport passage of the second transportsystem H2 in the second chamber apparatus CH2.

The first transport system H1 has the following function. That is, thesubstrate P before being subjected to the exposure process is loaded onthe substrate stage PST of the main exposure apparatus body EX. Further,the substrate P after being subjected to the exposure process isunloaded out of the substrate stage PST of the main exposure apparatusbody EX. The substrate P, which is subjected to the coating process withthe photosensitive material by the coating unit of the maincoater/developer body C/D, is subjected to the predetermined processesby the immersion unit 30 and the temperature regulation mechanism 40.After that, the substrate P is delivered to the first transport systemH1 via the interface IF by the second transport system H2. In thisarrangement, openings and shutters for opening/closing the openings areprovided at portions of the first and second chamber apparatuses CH1,CH2 allowed to face the interface IF respectively. The shutter is openedduring the transport operation of the substrate P with respect to theinterface IF. The substrate P before being subjected to the exposureprocess is loaded by the first transport system H1 on the substratestage PST of the main exposure apparatus body EX. The substrate P afterbeing subjected to the exposure process is unloaded out of the substratestage PST by the first transport system H1. The first transport systemH1 delivers the unloaded substrate P to the second transport system H2of the coater/developer apparatus C/D-SYS via the interface IF. Thesecond transport system H2 transports the substrate P after beingsubjected to the exposure process to the developing unit of the maincoater/developer body C/D. The development process is performed to thedelivered substrate P by the developing unit of the maincoater/developer body C/D.

Next, an explanation will be made about the main exposure apparatus bodyEX with reference to FIG. 2. FIG. 2 shows a schematic arrangementillustrating the main exposure apparatus body EX. With reference to FIG.2, the main exposure apparatus body EX includes a mask stage MST whichis movable while retaining a mask M, a substrate stage PST which has thesubstrate holder PH for holding the substrate P and which is capable ofmoving the substrate holder PH that holds the substrate P, anillumination optical system IL which illuminates, with an exposure lightbeam EL, the mask M retained by the mask stage MST, and a projectionoptical system PL which projects an image of a pattern of the mask Milluminated with the exposure light beam EL onto the substrate P.

The main exposure apparatus body EX of this embodiment is a liquidimmersion exposure apparatus to which the liquid immersion method isapplied in order that the exposure wavelength is substantially shortenedto improve the resolution and the depth of focus is substantiallywidened. The main exposure apparatus body EX is provided with a liquidimmersion mechanism 100 which fills, with the first liquid LQ1, theoptical path space for the exposure light beam EL disposed on the imageplane side of the projection optical system PL. The liquid immersionmechanism 100 includes a nozzle member 70 which is provided in thevicinity of the image plane of the projection optical system PL andwhich has a supply port 12 for supplying the first liquid LQ1 and arecovery port 22 for recovering the first liquid LQ1, a liquid supplymechanism 10 which supplies the first liquid LQ1 to the image plane sideof the projection optical system PL via the supply port 12 provided forthe nozzle member 70, and a liquid recovery mechanism 20 which recoversthe first liquid LQ1 disposed on the image plane side of the projectionoptical system PL via the recovery port 22 provided for the nozzlemember 70. The nozzle member 70 is formed in an annular form so that afirst optical element LS1, which is included in a plurality of opticalelements for constructing the projection optical system PL and which isdisposed closest to the image plane of the projection optical system PL,is surrounded over the substrate P (substrate stage PST).

The main exposure apparatus body EX forms the liquid immersion area LRof the first liquid LQ1 locally on a part of the substrate P including aprojection area AR of the projection optical system PL by the firstliquid LQ1 supplied from the liquid supply mechanism 10 at least duringthe period in which the pattern image of the mask M is projected ontothe substrate P, the liquid immersion area LR being larger than theprojection area AR and smaller than the substrate P. Specifically, themain exposure apparatus body EX fills, with the first liquid LQ1, theoptical path space which is disposed between the lower surface LSA ofthe first optical element LS1 arranged closest to the image plane of theprojection optical system PL and the upper surface of the substrate Parranged on the image plane side of the projection optical system PL.The exposure light beam EL, which is allowed to pass through the mask M,is radiated onto the substrate P via the projection optical system PLand the first liquid LQ1 disposed between the projection optical systemPL and the substrate P. Accordingly, the projection exposure of thepattern of the mask M is performed on the substrate P. The control unitCONT locally forms the liquid immersion area LR of the first liquid LQ1on the substrate P such that a predetermined amount of the first liquidLQ1 is supplied onto the substrate P by using the liquid supplymechanism 10, and a predetermined amount of the first liquid LQ1disposed on the substrate P is recovered by using the liquid recoverymechanism 20.

The embodiment of the present invention will be explained as exemplifiedby a case of the use of the scanning type exposure apparatus (so-calledscanning stepper) as the main exposure apparatus body EX in which thesubstrate P is exposed with the pattern formed on the mask M whilesynchronously moving the mask M and the substrate P in mutuallydifferent directions (opposite directions) in the scanning directions.In the following explanation, the X axis direction resides in thesynchronous movement direction (scanning direction) for the mask M andthe substrate P in the horizontal plane, the Y axis direction(non-scanning direction) resides in the direction which is perpendicularto the X axis direction in the horizontal plane, and the Z axisdirection resides in the direction which is perpendicular to the X axisdirection and the Y axis direction and which is coincident with theoptical axis AX of the projection optical system PL. The directions ofrotation (inclination) about the X axis, the Y axis, and the Z axis aredesignated as θX, θY, and θZ directions respectively. The term“substrate” referred to herein includes those obtained by coating a basematerial such as a semiconductor wafer with a photosensitive material(resist), and the term “mask” includes a reticle formed with a devicepattern to be subjected to the reduction projection onto the substrate.

The illumination optical system IL includes, for example, an exposurelight source, an optical integrator which uniformizes the illuminance ofthe light flux radiated from the exposure light source, a condenser lenswhich collects the exposure light beam EL supplied from the opticalintegrator, a relay lens system, and a field diaphragm which sets theillumination area on the mask M illuminated with the exposure light beamEL. The predetermined illumination area on the mask M is illuminatedwith the exposure light beam EL having a uniform illuminancedistribution by means of the illumination optical system IL. Thoseusable as the exposure light beam EL radiated from the illuminationoptical system IL include, for example, emission lines (g-ray, h-ray,i-ray) radiated, for example, from a mercury lamp, far ultraviolet lightbeams (DUV light beams) such as the KrF excimer laser beam (wavelength:248 nm), and vacuum ultraviolet light beams (VUV light beams) such asthe ArF excimer laser beam (wavelength: 193 nm) and the F₂ laser beam(wavelength: 157 nm). In this embodiment, the ArF excimer laser beam isused.

In this embodiment, pure water is used as the first liquid LQ1 forforming the liquid immersion area LR. Not only the ArF excimer laser butalso the emission lines (g-ray, h-ray, i-ray) radiated, for example,from a mercury lamp and the far ultraviolet light beams (DUV lightbeams) such as the KrF excimer laser beam (wavelength: 248 nm) aretransmissive through pure water.

The mask stage MST is movable while retaining the mask M. The mask stageMST retains the mask M by means of the vacuum attraction (or theelectrostatic attraction). The mask stage MST is two-dimensionallymovable in the plane perpendicular to the optical axis AX of theprojection optical system PL, i.e., in the XY plane, and it is finelyrotatable in the θZ direction in a state in which the mask M isretained, in accordance with the driving of a mask stage-driving unitMSTD including a linear motor controlled by the control unit CONT. Amovement mirror 91, which is movable together with the mask stage MST,is provided on the mask stage MST. A laser interferometer 92 is providedat a position opposed to the movement mirror 91. The position in thetwo-dimensional direction and the angle of rotation in the θZ direction(including the angles of rotation in the θX and θY directions in somesituations as well) of the mask M on the mask stage MST are measured inreal-time by the laser interferometer 92. The result of the measurementof the laser interferometer 92 is outputted to the control unit CONT.The control unit CONT drives the mask stage-driving unit MSTD on thebasis of the result of the measurement obtained by the laserinterferometer 92 to thereby control the position of the mask M retainedby the mask stage MST.

The projection optical system PL projects the image of the pattern ofthe mask M onto the substrate P at a predetermined projectionmagnification β. The projection optical system PL includes a pluralityof optical elements. The optical elements are retained by a barrel PK.In this embodiment, the projection optical system PL is based on thereduction system having the projection magnification β which is, forexample, ¼, ⅕, or ⅛. The projection optical system PL may be based onany one of the 1× magnification system and the magnifying system. Theprojection optical system PL may be based on any one of the dioptricsystem, the catoptric system, and the cata-dioptric system. In thisembodiment, the first optical element LS1, which is included in theplurality of optical elements for constructing the projection opticalsystem PL and which is disposed closest to the image plane of theprojection optical system PL, is exposed from the barrel PK.

The substrate stage PST has a substrate holder PH which holds thesubstrate P. The substrate holder PH is movable on the base member BP onthe image plane side of the projection optical system PL. The substrateholder PH holds the substrate P, for example, by means of the vacuumattraction. A recess 96 is provided on the substrate stage PST. Thesubstrate holder PH for holding the substrate P is arranged in therecess 96. The upper surface 97 of the substrate stage PST other thanthe recess 96 is a flat surface (flat section) which has approximatelythe same height as that of (flush with) the upper surface of thesubstrate P held by the substrate holder PH.

The substrate stage PST is two-dimensionally movable in the XY plane onthe base member BP, and it is finely rotatable in the θZ direction in astate in which the substrate P is retained by the aid of the substrateholder PH, in accordance with the driving of the substrate stage-drivingunit PSTD including a linear motor or the like controlled by the controlunit CONT. Further, the substrate stage PST is also movable in the Zaxis direction, the θX direction, and the θY direction. Therefore, theupper surface of the substrate P supported by the substrate stage PST ismovable in the directions of six degrees of freedom in the X axis, Yaxis, Z axis, θX, θY, and θZ directions. A movement mirror 93, which ismovable together with the substrate stage PST, is secured to the sidesurface of the substrate stage PST. A laser interferometer 94 isprovided at a position opposed to the movement mirror 93. The positionin the two-dimensional direction and the angle of rotation of thesubstrate P on the substrate stage PST are measured in real time by thelaser interferometer 94. The exposure apparatus EX is provided with afocus/leveling-detecting system (not shown) based on the obliqueincidence system which detects the surface position information aboutthe upper surface of the substrate P supported by the substrate stagePST as disclosed, for example, in Japanese Patent Application Laid-openNo. 8-37149. The focus/leveling-detecting system detects the surfaceposition information about the upper surface of the substrate P(position information in the Z axis direction, and the information aboutthe inclination in the θX and θY directions of the substrate P). Asystem based on the use of an electrostatic capacity type sensor may beadopted for the focus/leveling-detecting system. The result of themeasurement performed by the laser interferometer 94 is outputted to thecontrol unit CONT. The result of the detection performed by thefocus/leveling-detecting system is also outputted to the control unitCONT. The control unit CONT drives the substrate stage-driving unit PSTDon the basis of the detection result of the focus/leveling-detectingsystem to adjust and match the upper surface of the substrate P withrespect to the image plane of the projection optical system PL bycontrolling the focus position (Z position) and the angle of inclination(θX, θY) of the substrate P. Further, the position control is performedin the X axis direction, the Y axis direction, and the θZ direction ofthe substrate P on the basis of the measurement result of the laserinterferometer 94.

Next, an explanation will be made about the liquid supply mechanism 10and the liquid recovery mechanism 20 of the liquid immersion mechanism100. The liquid supply mechanism 10 supplies the first liquid LQ1 to theimage plane side of the projection optical system PL. The liquid supplymechanism 10 is provided with a liquid supply unit 11 which is capableof feeding the first liquid LQ1, and a supply tube 13 which has one endconnected to the liquid supply unit 11. The other end of the supply tube13 is connected to the nozzle member 70. An internal flow passage(supply flow passage), which connects the supply port 12 and the otherend of the supply tube 13, is formed in the nozzle member 70. The liquidsupply unit 11 includes, for example, a tank for accommodating the firstliquid LQ1, a pressurizing pump, and a filter unit for removing anyforeign matter from the first liquid LQ1. The liquid supply operation ofthe liquid supply unit 11 is controlled by the control unit CONT. It isnot necessarily indispensable that the main exposure apparatus body EXis provided with all of the tank, the pressurizing pump, the filter unitand the like of the liquid supply mechanism 10. These components may bereplaced with the equipment of a factory or the like in which the mainexposure apparatus body EX is installed.

The liquid recovery mechanism 20 recovers the first liquid LQ1 disposedon the image plane side of the projection optical system PL. The liquidrecovery mechanism 20 includes a liquid recovery unit 21 which iscapable of recovering the first liquid LQ1, and a recovery tube 23 whichhas one end connected to the liquid recovery unit 21. The other end ofthe recovery tube 23 is connected to the nozzle member 70. An internalflow passage (recovery flow passage), which connects the recovery port22 and the other end of the recovery tube 23, is formed in the nozzlemember 70. The liquid recovery unit 21 is provided with, for example, avacuum system (suction unit) such as a vacuum pump or the like, agas/liquid separator for separating the recovered first liquid LQ1 fromthe gas, and a tank for accommodating the recovered first liquid LQ1. Itis not necessarily indispensable that the main exposure apparatus bodyEX is provided with all of the vacuum system, the gas/liquid separator,the tank and the like of the liquid recovery mechanism 20. Thesecomponents may be replaced with the equipment of a factory or the likein which the main exposure apparatus body EX is installed.

The supply port 12 for supplying the first liquid LQ1 and the recoveryport 22 for recovering the first liquid LQ1 are formed on the lowersurface 70A of the nozzle member 70. The lower surface 70A of the nozzlemember 70 is provided at the position opposed to the upper surface ofthe substrate P and the upper surface 97 of the substrate stage PST. Thenozzle member 70 is the annular member which is provided to surround theside surface of the first optical element LS1. A plurality of the supplyports 12 are provided on the lower surface 70A of the nozzle member 70to surround the first optical element LS1 of the projection opticalsystem PL (optical axis AX of the projection optical system PL). Therecovery port 22 is provided outside while being separated from thesupply ports 12 with respect to the first optical element LS1 on thelower surface 70A of the nozzle member 70. The recovery port 22 isprovided to surround the first optical element LS1 and the supply ports12.

The control unit CONT locally forms the liquid immersion area LR of thefirst liquid LQ1 on the substrate P by supplying a predetermined amountof the first liquid LQ1 onto the substrate P by using the liquid supplymechanism 10 and recovering a predetermined amount of the first liquidLQ1 disposed on the substrate P by using the liquid recovery mechanism20. When the liquid immersion area LR of the first liquid LQ1 is formed,the control unit CONT drives the liquid supply unit 11 and the liquidrecovery unit 21 respectively. When the first liquid LQ1 is fed from theliquid supply unit 11 under the control of the control unit CONT, thefirst liquid LQ1, which is fed from the liquid supply unit 11, isallowed to flow through the supply tube 13. After that, the first liquidLQ1 is supplied to the image plane side of the projection optical systemPL from the supply ports 12 via the supply flow passage of the nozzlemember 70. When the liquid recovery unit 21 is driven under the controlof the control unit CONT, the first liquid LQ1, which is disposed on theimage plane side of the projection optical system PL, is allowed to flowinto the recovery flow passage of the nozzle member 70 via the recoveryport 22. The first liquid LQ1 is allowed to flow through the recoverytube 23, and then the first liquid LQ1 is recovered by the liquidrecovery unit 21.

Next, an explanation will be made with reference to a flow chart shownin FIG. 3 about the operation of the device production system SYSprovided with the main exposure apparatus body EX as described above.

At first, the coating unit of the main coater/developer body C/D is usedto perform the coating process in which the base material including thesilicon wafer (semiconductor wafer) is coated with the photosensitivematerial (Step S1). In the coating process, the base material is coatedwith the photosensitive material, for example, by means of apredetermined coating method such as the spin coat method. Apredetermined pretreatment is performed for the base material beforecoating the base material with the photosensitive material. Thepretreatment includes, for example, a cleaning (washing) treatment forremoving any foreign matter from the base material, a drying treatmentfor drying the base material after the cleaning, and a surface-modifyingtreatment for improving the tight contact performance between the basematerial and the photosensitive material. The surface-modifyingtreatment includes, for example, a treatment in which the base materialis coated with hexamethyldisilazane (HMDS) or the like. As for thepretreatment, it is also allowable to coat the base material (lowersurface of the photosensitive material) with an anti-reflective film(bottom ARC (Anti-Reflective Coating)).

FIG. 4 shows an example of the substrate P after performing the coatingprocess in the main coater/developer body C/D. With reference to FIG. 4,the substrate P has the base material 1, and the photosensitive material2 with which a part of the upper surface 1A of the base material 1 iscoated. As described above, the base material 1 includes, for example,the silicon wafer. An area, which occupies almost all of the centralportion of the upper surface 1A of the base material 1, is coated withthe photosensitive material 2 to have a predetermined thickness (forexample, about 200 nm). On the other hand, the circumferential edgeportion 1As of the upper surface 1A of the base material 1 is not coatedwith the photosensitive material 2. The base material 1 is exposed atthe circumferential edge portion 1As of the upper surface 1A. The sidesurface 1C and the lower surface (back surface) 1B of the base material1 are not coated with the photosensitive material 2. In this embodiment,a chemical amplification type resist is used as the photosensitivematerial 2.

When the photosensitive material 2 is provided on the base material 1 bymeans of the predetermined coating method such as the spin coat method,the circumferential edge portion of the base material 1 is also coatedwith the photosensitive material 2. This portion makes contact with thetransport arm of the transport system for transporting the substrate Pand the rack or shelf (substrate support section) of the carrier forstoring the substrate P. It is feared that the photosensitive material2, which is disposed at the circumferential edge portion of the basematerial 1, may be exfoliated by the mechanical contact. If thephotosensitive material 2 is exfoliated, then the exfoliated matter notonly serves as the foreign matter to pollute the transport arm and thecarrier therewith, but there is also such a possibility that thepolluted matter makes contact with the clean substrate P again to expandthe pollution. Further, the following phenomenon may arise in somesituations. That is, a large amount of the photosensitive material 2 isprovided so that the photosensitive material 2 at the circumferentialedge portion of the base material 1 rises more upwardly than that at thecentral portion. The photosensitive material 2, which is disposed at thecircumferential edge portion of the base material 1, tends to beexfoliated with ease. The exfoliated photosensitive material 2 behavesas the foreign matter. If the foreign matter adheres onto the substrateP, the pattern transfer accuracy is affected thereby. Accordingly, atreatment (so-called “edge rinse”), in which the photosensitive material2 disposed at the circumferential edge portion 1As is removed by using,for example, a solvent, is performed before performing the exposureprocess after providing the photosensitive material 2 on the basematerial 1 by means of the predetermined coating method. Accordingly,the photosensitive material 2 is removed at the circumferential edgeportion of the base material 1 (substrate P). The base material 1 isexposed at the circumferential edge portion 1As as shown in FIG. 4.

The heat treatment (pre-baking) is performed for the substrate P (Step2) after performing the coating process for coating the base material 1with the photosensitive material 2. The solvent, which remains in thephotosensitive material 2, is volatilized by means of the pre-baking.

Subsequently, the immersion process is performed, in which the substrateP is immersed in the second liquid LQ2 (Step S3). The immersion processis performed by the immersion unit 30 provided for the coater/developerapparatus C/D-SYS. The immersion unit 30 immerses the substrate P in thesecond liquid LQ2 under a preset predetermined immersion condition onthe basis of the information about the substrate P.

FIG. 5 shows the immersion unit 30. With reference to FIG. 5, theimmersion unit 30 is provided with a holder 31 which holds a centralportion of the lower surface of the substrate P (lower surface 1B of thebase material 1), a shaft 33 which is connected to the holder 31, arotating mechanism 32 which rotates the holder 31 that holds thesubstrate P by the aid of the shaft 33, a ring-shaped member 34 which isprovided to surround the circumference of the substrate P held by theholder 31 in order to avoid the scattering of the liquid, and a liquidsupply unit 36 which supplies the second liquid LQ2 onto the substrate Pvia a supply port 35A of a supply member 35. The substrate P, to whichthe pre-baking has been applied, is loaded on the holder 31 by thesecond transport system H2. Vacuum attraction holes, which constituteparts of a vacuum unit, are provided on the upper surface of the holder31. The holder 31 attracts and holds the central portion of the lowersurface of the substrate P. The rotating mechanism 32 includes anactuator such as a motor. The rotating mechanism 32 rotates thesubstrate P held by the holder 31 by rotating the shaft 33 connected tothe holder 31. The rotating mechanism 32 rotates the holder 31 whichholds the substrate P in the θZ direction in FIG. 5 at a predeterminednumber of revolutions per unit time. The supply member 35 is arrangedover the substrate P held by the holder 31, which has the supply port35A for supplying the second liquid LQ2. The second liquid LQ2, which isfed from the liquid supply unit 36, is supplied to the upper surface ofthe substrate P from the position over the substrate P via the supplyport 35A of the supply member 35. The supply member 35 is movable in thedirections of X axis, Y axis, Z axis, θX, θY, and θZ by means of anunillustrated driving mechanism. That is, the supply member 35 ismovable relatively with respect to the substrate P held by the holder31. The immersion unit 30 is capable of immersing the entire surface ofthe substrate P in the second liquid LQ2 by relatively moving the supplymember 35 with respect to the substrate P. The immersion unit 30 iscapable of adjusting, for example, the direction of the supply of thesecond liquid LQ2 to the substrate P and the distance between the supplyport 35A and the substrate P by relatively moving the supply member 35with respect to the substrate P. Further, the liquid supply unit 36 iscapable of supplying the second liquid LQ2 onto the substrate Pcontinuously or intermittently via the supply port 35A of the supplymember 35. The liquid supply unit 36 is capable of adjusting, forexample, the temperature of the second liquid LQ2 to be supplied and theamount (including the flow rate and the flow velocity) of the secondliquid LQ2 to be supplied per unit time. The relative movement betweenthe supply member 35 and the substrate P is not limited to the movementof the supply member 35. The substrate P may be moved, or both of thesupply member 35 and the substrate P may be moved.

The immersion unit 30 supplies the second liquid LQ2 from the supplyport 35A of the supply member 35 to the substrate P held by the holder31 so that the substrate P is immersed in the second liquid LQ2. Thephotosensitive material 2, with which the upper surface 1A of the basematerial 1 of the substrate P is coated, is sufficiently immersed in thesecond liquid LQ2 supplied from the supply member 35.

In this embodiment, the immersion unit 30 continuously supplies thesecond liquid LQ2 from the supply member 35 while relatively moving thesupply member 35 in the X axis direction with respect to the substrate Pretained by the holder 31 while rotating, in the θZ direction in FIG. 5,the substrate P retained by the holder 31 by means of the rotatingmechanism 32. Accordingly, the second liquid LQ2 is supplied to thesubstantially entire upper surface of the substrate P. Therefore, theimmersion unit 30 is capable of immersing the substantially entiresurface of the photosensitive material 2 with the second liquid LQ2. Thering-shaped member 34 is provided around the substrate P retained by theholder 31. Therefore, the scattering of the second liquid LQ2, which iscaused by the rotation of the substrate P, can be avoided by thering-shaped member 34.

In this embodiment, the second liquid LQ2, which is used for theimmersion process, is the same as the first liquid LQ1 which is used toform the liquid immersion area LR formed on the substrate P in order toperform the liquid immersion exposure process. That is, in thisembodiment, the second liquid LQ2 is pure (purified) water which ismanaged to have a predetermined purity (cleanness) and a predeterminedtemperature in the same manner as the first liquid LQ1. It is a matterof course that the second liquid LQ2 may be different from the firstliquid LQ1 provided that the substance, which is to be eluted when thesubstrate P is immersed in the first liquid LQ1, can be previouslyeluted. For example, ozone water can be used as the second liquid LQ2.

FIG. 6 schematically shows a state in which the photosensitive material2 of the substrate P is immersed in the second liquid LQ2. As describedabove, the photosensitive material 2 of this embodiment is the chemicalamplification type resist. The chemical amplification type resistincludes a base resin, a photo acid generator (PAG) which is containedin the base resin, and an amine-based substance which is called“quencher”. When such a photosensitive material 2 makes contact with theliquid, parts of the components of the photosensitive material 2,specifically, for example, PAG and the amine-based substance are elutedinto the liquid. In the following description, the substance (forexample, PAG and the amine-based substance), which is contained in thephotosensitive material 2 and which is possibly eluted into the liquid(LQ1, LQ2), is appropriately referred to as “predetermined substance”.

With reference to FIG. 6, the photosensitive material 2 is immersed inthe second liquid LQ2. It is assumed that the predetermined substancesuch as PAG and the amine-based substance is eluted into the secondliquid LQ2. When the upper surface of the photosensitive material 2makes contact with the second liquid LQ2, the predetermined substance(for example, PAG and the amine-based substance), which exists in afirst area 2U having a predetermined thickness (for example, about 5 to10 nm) from the upper surface of the photosensitive material 2, iseluted into the second liquid LQ2. However, the predetermined substance,which exists in a second area 2S as an underlying layer thereof, is noteluted into the second liquid LQ2 substantially. After a predeterminedperiod of time (for example, about several seconds to several tenssecond) elapses after the contact between the upper surface of thephotosensitive material 2 and the second liquid LQ2, the predeterminedsubstance, which is eluted from the first area 2U to the second liquidLQ2, is substantially absent. That is, after the predetermined period oftime elapses after the contact between the upper surface of thephotosensitive material 2 and the second liquid LQ2, a state is given,in which almost all of the predetermined substance existing in the firstarea 2U of the photosensitive material 2 is eluted and exhausted. Thepredetermined substance is hardly eluted from the photosensitivematerial 2 to the second liquid LQ2. The predetermined period of timechanges depending on the photosensitive material 2.

Therefore, even when the liquid immersion area LR of the first liquidLQ1 is formed on the substrate P (photosensitive material 2) is formedafter being immersed in the second liquid LQ2 for the predeterminedperiod of time, the predetermined substance is hardly eluted from thesubstrate P (photosensitive material 2) to the first liquid LQ1 asdescribed later on.

After the immersion process is performed for the substrate P, theremoval process is performed for the second liquid LQ2 on the substrateP (Step S4). When the removal process is performed for the second liquidLQ2, the immersion unit 30 stops the supply of the second liquid LQ2 bythe liquid supply unit 36, or the immersion unit 30 gradually decreasesthe supply amount, while the holder 31, which holds the substrate P, isrotated by the rotating mechanism 32. The immersion unit 30 rotates thesubstrate P at a predetermined number of revolutions per unit time byusing the rotating mechanism 32. Accordingly, the second liquid LQ2,which has been adhered to the substrate P, is scattered and removed fromthe substrate P by means of the action of the centrifugal force. Thatis, in this embodiment, the immersion unit 30 also has the function asthe liquid removal mechanism for removing the second liquid LQ2.

In Step S3, the immersion condition for performing the immersion processfor the substrate P is set depending on the information about thesubstrate P. The immersion condition includes the immersion time forimmersing the substrate P in the second liquid LQ2, i.e., the timeranging from the contact of the second liquid LQ2 with the substrate Pin Step S3 to the removal of the second liquid LQ2 from the surface ofthe substrate P in Step S4. The information about the substrate Pincludes the information about the photosensitive material 2. Theinformation about the photosensitive material 2 includes the informationabout the material for forming the photosensitive material 2, and theelution time of a part of the predetermined substance of thephotosensitive material 2 into the second liquid LQ2. The material forforming the photosensitive material 2 includes, for example, the baseresin, PAG, and the amine-based substance as described above. The periodof time (elution time), which ranges from the contact between thephotosensitive material 2 and the second liquid LQ2 to the elution ofalmost all of the predetermined substance from the photosensitivematerial 2 (first area 2U of the photosensitive material 2), changesdepending on, for example, the physical property of the material forforming the photosensitive material 2, and the content of thepredetermined substance such as PAG. The period of time (elution time),which ranges from the contact between the photosensitive material 2 andthe second liquid LQ2 to the start of the elution of the predeterminedsubstance, also changes depending on the photosensitive material 2.Therefore, when the immersion condition, which includes the immersiontime, is optimally set depending on the information about the substrateP including the information about the photosensitive material 2, almostall of the predetermined substance as described above can be eluted fromthe photosensitive material 2 (first area 2U) into the second liquidLQ2.

The immersion condition also includes the removal condition for thesecond liquid LQ2. The removal condition for the second liquid LQ2 isexemplified, for example, by the number of revolutions (velocity ofrotation) per unit time of the substrate P brought about by the rotatingmechanism 32, the rotation acceleration, and the time (rotation time) inwhich the rotation of the substrate P is executed. Further, the removalcondition for the second liquid LQ2 also includes, for example, therotation velocity profile and the rotation acceleration profile of therotating mechanism 32. The time (i.e., the immersion time) in which thesecond liquid LQ2 makes contact with the substrate P and the behavior(for example, the movement velocity) of the second liquid LQ2 on thesubstrate P change depending on the removal condition for the secondliquid LQ2. Therefore, when the removal condition for the second liquidLQ2 is optimally set depending on the information about the substrate P,almost all of the predetermined substance as described above can beeluted from the photosensitive material 2 (first area 2U) into thesecond liquid LQ2.

The immersion condition also includes the temperature of the secondliquid LQ2 to be supplied. In the case of the procedure in which thesecond liquid LQ2 is supplied to the substrate P from the supply port35A of the supply member 35 as in this embodiment, the immersioncondition also includes the amount (including the flow rate and the flowvelocity) per unit time of the second liquid LQ2 to be supplied, thesupply pressure to be applied when the second liquid LQ2 is supplied,and the direction in which the second liquid LQ2 is allowed to flow withrespect to the substrate P.

When the substrate P is immersed in the liquid (LQ1, LQ2), there is sucha possibility that a part of the substance for constructing the basematerial 1 may be eluted into the liquid depending on the type of thesubstance for constructing the base material 1, without being limited tothe predetermined substance contained in the photosensitive material 2.Therefore, the immersion unit 30 can also regard the possibility of theimmersion of the base material 1 in the liquid (LQ1, LQ2) and theinformation about the material (substance) for forming the base material1 as the information about the substrate P.

In this procedure, the immersion unit 30 supplies the second liquid LQ2onto the substrate P while rotating the substrate P. However, it ispossible to adopt any arrangement provided that the substrate P(photosensitive material 2) can be immersed in the second liquid LQ2.For example, a liquid bath may be previously filled with the secondliquid LQ2, and the substrate P may be immersed in the second liquid LQ2in the liquid bath. Alternatively, the substrate P may be immersed inthe second liquid LQ2 by supplying the second liquid LQ2 to thesubstrate P so that the second liquid LQ2 is allowed to blow against thesubstrate P. In the case of the procedure in which the second liquid LQ2is allowed to blow against the substrate P, the immersion condition alsoincludes the pressure to be applied when the second liquid LQ2 isallowed to blow. The immersion condition is set depending on theinformation about the substrate P as well.

As shown in FIG. 7, the following arrangement may be also adopted forthe liquid removal mechanism 39 for removing the second liquid LQ2 onthe substrate P. That is, blow members 37, 38 having blow ports 37A,38A, which allow the gas to blow therefrom, may be arranged on the uppersurface side and the lower surface side of the substrate P respectively.The liquid removal mechanism 39 removes the second liquid LQ2 adhered tothe substrate P by means of the force of the gas allowed to blow fromthe blow members 37, 38. When the second liquid LQ2 is removed by usingthe liquid removal mechanism 39, for example, the pressure and the gassupply amount (flow velocity) per unit time of the gas allowed to blowfrom the blow ports 37A, 38A can be also used as the immersion condition(removal condition).

After the second liquid LQ2 is removed from the substrate P, thetemperature of the substrate P is adjusted by the temperature adjustmentmechanism 40 (Step S5). When the second liquid LQ2, which remains on thesubstrate P, is removed by using the liquid removal mechanism 39, thereis such a possibility that the temperature of the substrate P may bechanged due to the heat of vaporization of the second liquid LQ2 toprovide any temperature different from the desired temperature.Therefore, the temperature adjustment mechanism 40 adjusts thetemperature of the substrate P in order to compensate the temperaturechange of the substrate P due to the heat of vaporization brought aboutwhen the second liquid LQ2 is removed. The temperature of the substrateP is adjusted so that the temperature is approximately same as thetemperature of the substrate holder PH and/or the temperature of thefirst liquid LQ1. When the temperature of the substrate P is adjusted sothat the temperature is approximately same as the temperature of thesubstrate holder PH, it is possible to suppress the expansion and thecontraction of the substrate P which would be otherwise caused by thetemperature change of the substrate P when the substrate P is loaded onthe substrate holder PH. When the temperature of the substrate P isadjusted so that the temperature is approximately the same as thetemperature of the first liquid LQ1, then it is possible to suppress theexpansion and contraction of the substrate P which would be otherwisecaused by the temperature change of the substrate P, and it is possibleto suppress the temperature change of the first liquid LQ1 when theliquid immersion area LR of the first liquid LQ1 is formed on thesubstrate P.

FIG. 8 shows the temperature regulation mechanism 40. With reference toFIG. 8, the temperature adjustment mechanism 40 includes a holder 41which holds the substrate P, a temperature adjustment unit 42 whichincludes a heating unit and a cooling unit provided in the holder 41, atemperature sensor 43 which measures the temperature of the substrate Pheld by the holder 41, and a temperature control unit 44 which adjuststhe temperature of the holder 41 that holds the substrate P on the basisof the measurement result of the temperature sensor 43 by the aid of thetemperature adjustment unit 42. The substrate P, which has beensubjected to the immersion process, is loaded on the holder 41 by meansof the second transport system H2. The temperature control unit 44 ofthe temperature adjustment mechanism 40 adjusts the temperature of theholder 41 by the aid of the temperature adjustment unit 42 on the basisof the measurement result of the temperature sensor 43 in a state inwhich the substrate P is held by the holder 41. Accordingly, thesubstrate P, which is held by the holder 41, can be adjusted to have adesired temperature.

As shown in FIG. 9, the following arrangement is also available. Thatis, a temperature adjustment mechanism 40′ includes an accommodatingchamber 45 which is capable of accommodating the substrate P, and atemperature adjustment unit 46 which adjusts the temperature in theaccommodating chamber 45. The substrate P is arranged in theaccommodating chamber 45 adjusted to have a desired temperature. Asdescribed above, the substrate P may be arranged in the atmosphereadjusted to have the desired temperature. Alternatively, the temperatureof the substrate P may be adjusted by allowing the gas adjusted to havea predetermined temperature against the substrate P from the blowmembers 37, 38 as shown in FIG. 7.

The holder 31 of the immersion unit 30 as explained with reference toFIG. 5 may be allowed to have the temperature-adjusting function capableof adjusting the temperature of the held substrate P. The temperature ofthe substrate P may be adjusted by using the holder 31 of the immersionunit 30 after removing the second liquid LQ2 from the substrate P.Alternatively, the temperature of the substrate P may be adjusted byusing the holder 31 of the immersion unit 30 before removing the secondliquid LQ2 in consideration of the temperature change of the substrate Pcaused by the heat of vaporization brought about when the second liquidLQ2 is removed. In this procedure, the immersion unit 30 previouslystores the relationship between the information about the second liquidLQ2 including, for example, the removal condition and the physicalproperty of the second liquid LQ2 to be used and the temperature changeof the substrate P caused by the heat of vaporization brought about whenthe second liquid LQ2 is removed. The relationship can be previouslydetermined, for example, by an experiment or simulation. The immersionunit 30 can predict the temperature change of the substrate P caused bythe heat of vaporization brought about when the second liquid LQ2 isremoved, on the basis of the stored relationship and the removalcondition under which the removal process is executed for the secondliquid LQ2. The immersion unit can provide a desired value of thetemperature of the substrate P after removing the second liquid LQ2 byadjusting the temperature of the substrate P before removing the secondliquid LQ2 from the substrate P on the basis of the predicted result.For example, the immersion unit 30 can set the temperature of thesubstrate P so that the temperature is higher than a desired value inconsideration of the decrease in the temperature of the substrate Pcaused by the heat of vaporization brought about when the second liquidLQ2 is removed. Of course, the temperature of the substrate P, which iscaused by the heat of vaporization brought about when the second liquidLQ2 is removed in the immersion unit 30, may be compensated by adjustingthe temperature of the substrate P before placing the substrate P on theholder 31 of the immersion unit 30.

After the temperature of the substrate P is adjusted, the secondtransport system H2 unloads the substrate P out of the temperatureregulation mechanism 40. The substrate P is delivered via the interfaceIF to the first transport system H1 of the exposure apparatus EX-SYS.The first transport system H1 transports (loads) the substrate P ontothe substrate holder PH of the main exposure apparatus body EX (StepS6).

The control unit CONT of the exposure apparatus EX-SYS forms the liquidimmersion area LR of the first liquid LQ1 on the substrate P in thestate of being held by the substrate holder PH, by using the liquidimmersion mechanism 100. The control unit CONT radiates the exposurelight beam EL onto the substrate P in the state of being held by thesubstrate holder PH through the first liquid LQ1 to perform the liquidimmersion exposure for the substrate P (Step S7).

FIG. 10 shows a state wherein the substrate P, which is held by thesubstrate holder PH of the substrate stage PST, is subjected to theliquid immersion exposure. With reference to FIG. 10, the substratestage PST has the recess 96. The substrate holder PH for holding thesubstrate P is provided inside the recess 96. The substrate holder PHincludes a base member 80 which has a bottom surface portion 80B opposedto the lower surface of the substrate P (lower surface 1B of the basematerial 1) while being away therefrom by a predetermined distance, acircumferential wall portion 81 which is formed on the base member 80and which has an upper surface 81A opposed to the lower surface of thesubstrate P, and support portions 82 which are formed on the bottomsurface 80B disposed inside the circumferential wall portion 81. Thecircumferential wall portion 81 is formed to be substantially annular inconformity with the shape of the substrate P. The upper surface 81A ofthe circumferential wall portion 81 is formed opposingly to thecircumferential edge portion of the lower surface of the substrate P.The upper surface 81A of the circumferential wall portion 81 is a flatsurface. The plurality of support portions 82 of the substrate holder PHare provided uniformly at the inside of the circumferential wall portion81. The support portions 82 include a plurality of support pins. Thesubstrate holder PH has the so-called pin-chuck mechanism. The pin-chuckmechanism of the substrate holder PH includes a suction mechanism whichis provided with suction ports 84 for providing the negative pressure inthe space 83 surrounded by the base member 80 of the substrate holderPH, the circumferential wall portion 81, and the substrate P. Thesubstrate P is attracted and held by the support portions 83 byproviding the negative pressure in the space 83. The plurality ofsuction ports 84 are provided uniformly on the bottom surface 80B of thebase member 80. A gap A, which has a distance of about 0.1 to 1.0 mm, isformed between the side surface of the substrate P (side surface 1C ofthe base material 1) held by the substrate holder PH and the inner sidesurface 96A of the recess 96 of the substrate stage PST provided aroundthe substrate P. In this embodiment, the upper surface 81A of thecircumferential wall portion 81 is the flat surface. The upper surface81A is coated with a liquid-repellent material such as a fluorine-basedrein material to have the liquid repellence. A predetermined gap B isformed between the upper surface 81A of the circumferential wall portion81 and the lower surface of the substrate P.

In this embodiment, the substrate P is immersed in the second liquid LQ2in Step S3 before radiating the exposure light beam EL onto thesubstrate P through the first liquid LQ1. Therefore, even when the firstliquid LQ1 is allowed to make contact again with the photosensitivematerial 2 subjected to the immersion process with the second liquid LQ2as described above, the predetermined substance (for example, PAG) isscarcely eluted from the photosensitive material 2 to the first liquidLQ1.

PAG is scarcely present in the first area 2U of the photosensitivematerial 2. However, as schematically shown in FIG. 11, the exposurelight beam EL, which is radiated onto the photosensitive material 2 ofthe substrate P, can pass through the first area 2U to arrive at thesecond area 2S in which PAG is present.

After the completion of the liquid immersion exposure for the substrateP, the control unit CONT stops the supply of the first liquid LQ1 by theliquid supply mechanism 10. Further, the control unit CONT continues thedriving of the liquid recovery mechanism 20 to recover and remove thefirst liquid LQ1 on the substrate P and the substrate stage PST.Subsequently, the control unit CONT unloads the substrate P out of thesubstrate holder PH by using the first transport system H1.

The substrate P, which is unloaded out of the substrate holder PH andwhich has been subjected to the exposure process, is subjected to a heattreatment (post-baking) called PEB (Post Exposure Bake) (Step S8). Inthe case of the chemical amplification type resist, acid is generatedfrom PAG by being irradiated with the exposure light beam EL. When thepost-baking is performed for the chemical amplification type resistafter being irradiated with the exposure light beam EL, the alkalisolubility is expressed in the area corresponding to the radiation areaof the exposure light beam EL (pattern of the mask M). The post-bake canbe performed for the substrate P by using the temperature adjustmentmechanism 40 provided for the coater/developer apparatus C/D-SYS asexplained with reference to, for example, FIGS. 8 and 9. Therefore, thesubstrate P, for which the exposure process has been completed, isunloaded out of the substrate holder PH by the first transport systemH1, and then the substrate P is delivered to the second transport systemH2 via the interface IF. The second transport system H2 loads thesubstrate P to the holder 41 of the temperature adjustment mechanism 40.The temperature adjustment mechanism 40 performs the post-baking for thesubstrate P loaded on the holder 41. In this embodiment, the temperatureadjustment mechanism 40 is used to perform both of the post-bakingprocess after the exposure for the substrate P and the temperatureadjustment for the substrate P after removing the liquid by means of theliquid removal mechanism. However, it is a matter of course that theseprocedures may be performed with distinct temperature adjustmentmechanisms respectively.

FIG. 12 schematically shows the behavior of the photosensitive material2 for which the post-baking (PEB) is performed. Owing to the immersionprocess performed in Step S3, PAG scarcely exists in the first area 2Uof the photosensitive material 2. Therefore, any acid, which resultsfrom PAG, is hardly generated in the first area 2U of the photosensitivematerial 2 after radiating the exposure light beam EL onto thephotosensitive material 2. On the other hand, a sufficient amount of PAGexists in the second area 2S of the photosensitive material 2.Therefore, a sufficient amount of acid is generated from PAG in thesecond area 2S by being irradiated with the exposure light beam EL. Whenthe post-baking is performed to the substrate P including thephotosensitive material 2 in the state as described above, a phenomenonoccurs as shown in FIG. 12, in which the acid, which exists in thesecond area 2S, is diffused to the first area 2U. That is, the acid isscarcely present in the first area 2U after the exposure. However, whenthe post-baking is performed, the first area 2U is supplemented with theacid existing in the second area 2S. When the post-baking is furthercontinued in the state in which the first area 2U is supplemented withthe acid, it is possible to express the alkali solubility in the area ofthe photosensitive material 2 corresponding to the radiation area of theexposure light beam EL (pattern of the mask M).

The substrate P, to which the post-baking has been performed, istransported to the main coater/developer body C/D by the secondtransport system H2, and the development process is performed therefor(Step S9).

As explained above, the substrate P is immersed in the second liquid LQ2before radiating the exposure light beam EL onto the substrate P throughthe first liquid LQ1. Accordingly, it is possible to suppress theelution of the predetermined substance such as PAG into the first liquidLQ1 of the liquid immersion area LR during the liquid immersion exposurefor the substrate P. If the predetermined substance such as PAG iseluted into the first liquid LQ1, the first liquid LQ1 is polluted, andthe polluted first liquid LQ1 is dried, then it is feared that theadhesion trace (water mark), which results from the predeterminedsubstance, may be formed on the substrate P. However, substantially nopredetermined substance is eluted from the substrate P into the firstliquid LQ1 of the liquid immersion area LR. Therefore, even when thefirst liquid LQ1, which remains on the substrate P, is dried, it ispossible to suppress the occurrence of the inconvenience which would beotherwise caused such that the adhesion trace is formed on the substrateP.

The inconvenience of the formation of the adhesion trace on thesubstrate P including the photosensitive material 2 is avoided.Accordingly, even when the development process is performed, it ispossible to avoid the occurrence of the pattern defect. Therefore, it ispossible to produce the device having the desired performance.

The pollution (contamination) of the first liquid LQ1 of the liquidimmersion area LR is avoided. Therefore, it is also possible to avoidthe pollution of, for example, the nozzle member 70 to make contact withthe first liquid LQ1, the first optical element LS1, the upper surface97 of the substrate stage PST, the substrate holder PH, and the opticalmeasuring unit provided on the upper surface 97 of the substrate stagePST. It is possible to accurately perform the exposure process and themeasurement process.

In Step S3, the predetermined substance such as PAG is eluted into thesecond liquid LQ2 in which the substrate P is immersed. The secondliquid LQ2 is polluted with the predetermined substance. However, inStep S4, the second liquid LQ2 is removed from the substrate P.Therefore, it is possible to avoid the generation of the foreign matter(adhered matter) on the substrate P. When the liquid is removed from thesubstrate P after cleaning out the polluted second liquid LQ2 with theclean second liquid LQ2, it is possible to suppress the generation ofthe foreign matter (adhered matter) on the substrate P even when theremaining second liquid LQ2 is dried, because the concentration of thepollutant (eluted matter) is lowered in the second liquid LQ2, even ifdroplets or the like of the second liquid LQ2 remain on the substrate P.

In this embodiment, the immersion unit 30 is provided for thecoater/developer apparatus C/D-SYS. However, it is a matter of coursethat the immersion unit 30 is provided for the exposure apparatusEX-SYS. For example, the immersion unit 30 may be provided at anintermediate position of the transport passage of the first transportsystem H1 for constructing the exposure apparatus EX-SYS. Accordingly,the substrate P before the liquid immersion exposure process can beimmersed in the second liquid LQ2 in the exposure apparatus EX-SYS.Alternatively, the immersion unit 30 may be provided for the interfaceIF. On the other hand, the temperature adjustment mechanism 40 may beprovided for the exposure apparatus EX-SYS as well. Accordingly, thetemperature of the substrate P can be adjusted by using the temperatureadjustment mechanism 40 in order to compensate the temperature change ofthe substrate P caused by the heat of vaporization brought about whenthe second liquid LQ2 is removed in the exposure apparatus EX-SYS. Thetemperature adjustment mechanism 40 can be also provided at anintermediate position of the transport passage of the first transportsystem H1, in the same manner as the immersion unit 30. It is a matterof course that the temperature adjustment mechanism 40 can be providedfor the interface IF as well.

It is desirable that the temperature adjustment mechanism 40 isinstalled in the vicinity of the immersion unit 30 (liquid removalmechanism). However, the immersion unit 30 may be arranged for thecoater/developer apparatus C/D-SYS, and the temperature adjustmentmechanism 40 may be arranged for the exposure apparatus EX-SYS.

The temperature adjustment may be omitted after the immersion processwhen it is unnecessary to compensate the temperature change of thesubstrate P caused by the heat of vaporization and/or when thetemperature change of the substrate P, which is caused by the heat ofvaporization, is small to an allowable extent.

In this embodiment, the immersion unit 30 is provided at theintermediate position of the transport passage of the transport system H(H1, H2). The substrate P is immersed in the second liquid LQ2 beforeholding the substrate P by the substrate holder PH. However, the liquidimmersion mechanism 100 may be allowed to have the function as theimmersion unit, and the substrate P may be immersed in the first liquidLQ1 after holding the substrate P by the substrate holder PH. That is,the following step may be provided. The substrate P is loaded and heldby the substrate holder PH, and then the first liquid LQ1 is suppliedonto the substrate P from the supply port 12 of the nozzle member 70before starting the liquid immersion exposure for the substrate P. Thesubstrate P is immersed by using the supplied first liquid LQ1. Thecontrol unit CONT supplies and recovers the first liquid LQ1 via therecovery port 22 and the supply port 12 of the nozzle member 70, whilethe substrate P, which is held by the substrate holder PH, is relativelymoved in the XY directions with respect to the nozzle member 70.Accordingly, a wide area of the upper surface of the substrate P can beimmersed with the first liquid LQ1. After the completion of theimmersion process, the control unit CONT recovers (removes) the firstliquid LQ1 from the substrate P by using the liquid recovery mechanism20. After the completion of the removal of the first liquid LQ1, theliquid immersion area LR of the first liquid LQ1 is formed again on thesubstrate P by using the liquid immersion mechanism 100. The substrate Pis exposed through the first liquid LQ1. When the arrangement asdescribed above is adopted, the immersion process can be performed forthe substrate P without providing the immersion unit 30 at theintermediate position of the transport passage of the transport systemH. Therefore, it is possible to simplify the apparatus structure, and itis possible to reduce the apparatus cost.

It is also desirable that the liquid immersion condition is optimized onthe basis of the information about the substrate P when the immersionprocess is performed by using the liquid immersion mechanism 100. It isnecessary that the liquid immersion condition is set so that any harmfulinfluence is not exerted, for example, on the first optical element LS1,when the immersion process is performed by using the liquid immersionmechanism 100. For example, when the immersion process is performed forthe substrate P by using the liquid immersion mechanism 100, it isappropriate that the supply amount and the recovery amount per unit timeof the first liquid LQ1 by the liquid immersion mechanism 100 are largerthan the supply amount and the recovery amount per unit time of thefirst liquid LQ1 during the liquid immersion exposure. Accordingly, itis possible to quicken the flow velocity of the first liquid LQ1 on thesubstrate P during the immersion process as compared with the flowvelocity of the first liquid LQ1 on the substrate P during the liquidimmersion exposure. Therefore, the pollutant, which is eluted into thefirst liquid LQ1, can be quickly recovered from the recovery port 22during the immersion process. It is possible to avoid the adhesion ofthe foreign matter resulting from the predetermined substance elutedfrom the substrate P, for example, on the substrate P, the upper surface97 of the substrate stage PST, and the first optical element LS1.

In the operation described above, all of the first liquid LQ1, whichforms the liquid immersion area LR, is recovered after the immersionprocess based on the use of the liquid immersion mechanism 100, and theliquid immersion area LR is formed again with the first liquid LQ1.However, the liquid immersion exposure process (exposure step) may beperformed continuously to the immersion process (immersion step) whileforming the liquid immersion area LR (for example, while continuing thesupply and the recovery of the liquid). In this procedure, the period oftime, in which the substrate is immersed in the first liquid, may bemanaged, and the exposure may be started after the elapse of time inwhich the predetermined substance is completely eluted. That is, theobject of the present invention can be also achieved by supplying theliquid onto the substrate P and starting the liquid immersion exposureafter the elapse of a period of time sufficient for the predeterminedsubstance to be eluted from the substrate P. However, it is desirablethat the cleaning or recovery operation for the liquid is performedwhile maintaining the liquid immersion area, because the elutedpredetermined substance is contained in the liquid.

In this embodiment, at least a part of the first liquid LQ1 (and/or thesecond liquid LQ2), which is recovered by the liquid recovery mechanism20, may be returned to the liquid supply mechanism 10. Alternatively,all of the first liquid LQ1 (or the second liquid LQ2), which isrecovered by the liquid recovery mechanism 20, may be discarded, and thenew clean first liquid LQ1 (and/or the second liquid LQ2) may besupplied from the liquid supply mechanism 10. The structure of theliquid immersion mechanism 1 including, for example, the nozzle member70 is not limited to the structure as described above. For example, itis also possible to use those described in European Patent PublicationNo. 1420298 and International Publication Nos. 2004/055803, 2004/057589,2004/057590, and 2005/029559.

The second liquid LQ2, which is distinct from the first liquid LQ1, maybe also used when the immersion process is performed by using the liquidimmersion mechanism 100.

In the first embodiment, it is possible to more effectively avoid thegeneration of the foreign matter (adhered matter) on the substrate P byarranging a liquid removal mechanism for removing the liquid remainingon the substrate P unloaded out of the substrate holder PH after theliquid immersion exposure for the substrate P having been subjected tothe immersion process. For example, as shown in FIG. 7, it is possibleto arrange the mechanism which removes the liquid by allowing the gas toblow against the front surface and the back surface of the substrate P.In this arrangement, the blow ports 37A, 38A for the gas may be arrangedin the vicinity of the circumference of the substrate P to remove onlythe liquid remaining in the vicinity of the circumferential edge of thesubstrate P by rotating the substrate P. In this case, a detection unit,which detects the liquid remaining on the substrate P unloaded out ofthe substrate holder PH after the liquid immersion exposure for thesubstrate P, may be arranged. When the liquid on the substrate P isdetected, the liquid removal operation may be executed for the substrateP by using the liquid removal mechanism as described above. In the firstembodiment described above, the substrate P is immersed in the secondliquid LQ2 before the exposure step, and substantially all of thepredetermined substance is eluted from the substrate P into the secondliquid LQ2. However, it is also allowable that substantially all of thepredetermined substance is not eluted from the substrate P into thesecond liquid LQ2, if permitted, on condition that the amount of elutionof the predetermined substance into the first liquid LQ1 is small.

Second Embodiment

Next, a second embodiment will be explained with reference to a flowchart shown in FIG. 13. In the following description, the constitutivecomponents, which are the same as or equivalent to those described inthe first embodiment, are designated by the same reference numerals, anyexplanation of which will be simplified or omitted.

The feature of the second embodiment resides in the fact that a cleaningprocess is performed to the substrate P after the completion of theliquid immersion exposure. The following explanation will be madeassuming that the immersion process is not performed for the substrate Pbefore performing the liquid immersion exposure for the substrate P.However, it is a matter of course that the cleaning process may beapplied as described below after performing the liquid immersionexposure for the substrate P to which the immersion process has beenapplied. That is, in the exposure apparatus and the exposure method ofthis embodiment, the immersion unit and the immersion step are notessential.

The liquid immersion process is performed to the substrate P in thestate in which the substrate P is held by the substrate holder PH (StepS7) in the same manner as in the embodiment described above.

After the completion of the liquid immersion exposure process, thecleaning process is performed for cleaning the substrate P while holdingthe substrate P by the substrate holder PH (Step 7.1). The control unitCONT moves the substrate P held by the substrate holder PH relativelywith respect to the nozzle member 70 to clean the substrate P with thefirst liquid LQ1 while the first liquid LQ1 is retained on the imageplane side of the projection optical system PL while supplying andrecovering the first liquid LQ1 by means of the liquid immersionmechanism 100.

The predetermined substance is eluted from the substrate P, especiallyfrom the photosensitive material thereof into the first liquid LQ1 ofthe liquid immersion area LR during the liquid immersion exposure forthe substrate P. It is feared that any foreign matter may be adheredonto the substrate P due to the predetermined substance (eluted matter)eluted into the first liquid LQ1. The control unit CONT can decrease orminiaturize (decompose, pulverize into fine particles, and/or convert tohave fine and minute sizes) or remove the foreign matter adhered ontothe substrate P resulting from the eluted matter eluted from thesubstrate P into the first liquid LQ1 by cleaning, with the first liquidLQ1, the substrate P after making the contact with the first liquid LQ1for forming the liquid immersion area LR. Therefore, it is possible toavoid the inconvenience which would be otherwise caused such that theadhesion trace is formed on the substrate P. The foreign matter, whichis adhered onto the substrate P resulting from the predeterminedsubstance (eluted matter) eluted into the first liquid LQ1, means the“predetermined substance” itself including the component of thephotosensitive material such as PAG and the amine-based substance asdescribed in the first embodiment as well as the substance generated bythe modification, the bonding, and/or the decomposition of the“predetermined substance” as described above. The substance as describedabove can be identified by detecting, for example, the functional groupinherent in PAG or the amine-based substance itself or any compoundthereof by means of an analysis method such as the infraredspectroscopic analysis and the TOF-SIMS analysis.

FIG. 14 shows a plan view schematically illustrating a state in whichthe substrate P is cleaned. The control unit CONT supplies the firstliquid LQ1 from the supply port 12 of the nozzle member 70 and recoversthe first liquid LQ1 from the recovery port 22 while relatively movingthe nozzle member 70 and the substrate P held by the substrate holder PHin the XY directions as indicated by the arrows y1, y2 shown in FIG. 14.Accordingly, the substantially entire region of the upper surface of thesubstrate P can be satisfactorily cleaned.

The base material 1 is exposed at the circumferential edge portion 1Asof the substrate P of this embodiment. Therefore, the control unit CONTpreponderantly cleans the circumferential edge portion 1As of thesubstrate P held by the substrate holder PH by using the first liquidLQ1 supplied from the supply port 12 of the nozzle member 70.

FIG. 15 shows a sectional view illustrating a state in which thecircumferential edge portion 1As of the substrate P is cleaned. When thecircumferential edge portion 1As of the substrate P is cleaned with thefirst liquid LQ1, the control unit CONT forms the liquid immersion areaLR of the first liquid LQ1 on the circumferential edge portion 1As ofthe substrate P. The nozzle member 70 and the substrate stage PST arerelatively moved, and the liquid immersion area LR of the first liquidLQ1 is moved along the circumferential edge portion 1As (gap A) which isformed to be substantially annular, as indicated by the arrow y3 shownin FIG. 14. The number of the movement of the liquid immersion area LRalong the arrow y3 is not limited to one (one round). The movement canbe executed arbitrarily a plurality of times (a plurality of rounds).

The base material 1 has the lyophilicity or liquid-attracting propertywith respect to the liquid LQ1 as compared with the photosensitivematerial 2 in many cases. Therefore, there is such a high possibilitythat the liquid LQ1, which is used for the liquid immersion exposure,remains on the side surface 1C and/or the circumferential edge portion1As as the exposed portion of the base material 1. Further, there issuch a high possibility that the first liquid LQ1, which remains on thecircumferential edge portion 1As, is dried, the foreign matter isadhered to the circumferential edge portion 1As of the base material 1,and the adhesion trace is formed. Accordingly, the circumferential edgeportion 1As of the base material 1 is preponderantly cleaned after theliquid immersion exposure. Thus, it is possible to avoid theinconvenience of the adhesion of the foreign matter to thecircumferential edge portion 1As of the substrate P. Consequently, it ispossible to avoid the inconvenience of the formation of the adhesiontrace. In other situations, even when the foreign matter is adhered tothe circumferential edge portion 1As, the foreign matter can bedecreased or miniaturized or removed. Further, it is possible to avoidthe adhesion of the foreign matter to the side surface of the substrateP (side surface 1C of the base material 1) by moving the liquidimmersion area LR of the first liquid LQ1 along the gap A. Even when theforeign matter is adhered, it is possible to decrease or miniaturize orremove the adhered foreign matter.

The cleaning process is performed for a predetermined period of time inthe state in which the substrate P is held by the substrate holder PH.After that, the control unit CONT recovers and removes the first liquidLQ1 used for the cleaning process, by using the liquid recoverymechanism 20 (Step S7.2). Subsequently, the substrate P, to which thecleaning process has been applied, is unloaded by the control unit CONTby using the first transport system H1. The pollution of the firsttransport system H1 is suppressed when the substrate P is unloaded,because the cleaning process has been performed for the substrate P onthe substrate holder PH. The post-baking (Step S8) and the developmentprocess (Step S9) are performed for the substrate P in the same manneras in the embodiment described above.

As described above, the cleaning process is performed for the substrateP by using the first liquid LQ1 supplied from the supply port 12 of thenozzle member 70 in the state in which the substrate P is held by thesubstrate holder PH before the substrate P, which has been subjected tothe exposure process, is unloaded out of the substrate holder PH.Therefore, it is possible to remove or decrease or miniaturize theforeign matter (adhered matter) adhered to the substrate P. Even whenthe droplets or the like of the first liquid LQ1 remain on the substrateP after the cleaning process, the concentration of the pollutant (elutedsubstance) is lowered in the first liquid LQ1 remaining on the substrateP owing to the cleaning process. Therefore, even when the remainingfirst liquid LQ1 is dried, it is possible to avoid (control) theappearance of the foreign matter (adhered matter) on the substrate P.Therefore, the pollution of the transport system H is not only avoided,but the occurrence of the pattern defect can be also avoided even whenthe development process is performed with the coater/developer apparatusC/D-SYS. It is also possible to avoid the pollution of thesubstrate-accommodating container when the substrate P is transported tothe substrate-accommodating container from the substrate stage PST(substrate holder PH). In particular, the circumferential edge portionof the substrate P is preponderantly cleaned in this embodiment.Therefore, it is possible to effectively avoid the pollution of thesubstrate-accommodating container and the transport system forsupporting the circumferential edge portion of the substrate P.

The second liquid LQ2, which is different from the first liquid LQ1, maybe used for the cleaning process in the second embodiment. In this case,the first liquid LQ1 may be recovered after the liquid immersionexposure process based on the use of the first liquid LQ1, and thesecond liquid LQ2 may be supplied and recovered by using the liquidimmersion mechanism 100. A liquid, which contains a component having thecleaning function, may be used for the second liquid LQ2. The secondliquid LQ2 may be prepared by containing, for example, a componenthaving the cleaning function such as a surfactant and/or a water-solubleorganic solvent in the liquid which is of the same type as that of thefirst liquid.

Third Embodiment

Next, a third embodiment will be explained. The feature of the thirdembodiment resides in the fact that the substrate P, for which theliquid immersion exposure has been completed, is unloaded out of thesubstrate holder PH, and then the substrate P is cleaned with the secondliquid LQ2. Also in this embodiment, the second liquid LQ2 for thecleaning process is the same as the first liquid LQ1 for the liquidimmersion exposure process.

FIG. 16 schematically shows a cleaning unit 50 for cleaning thesubstrate P after being unloaded out of the substrate holder PH. Thecleaning unit 50 is provided at an intermediate position of the secondtransport system H2 of the coater/developer apparatus C/D-SYS. Thecleaning unit 50 is capable of cleaning the upper surface of thesubstrate P and the lower surface of the substrate P (lower surface 1Bof the base material 1).

The cleaning unit 50 comprises a first supply member 51 which isarranged over the substrate P and which has a supply port 51A forsupplying the second liquid LQ2 to the upper surface of the substrate P,and a second supply member 52 which is arranged under the substrate Pand which has a supply port 52A for supplying the second liquid LQ2 tothe lower surface of the substrate P. The substrate P is held by anunillustrated holder. The first and second supply members 51, 52 and thesubstrate P are movable relatively to one another. When the secondliquid LQ2 is supplied to the substrate P from the first and secondsupply members 51, 52 while relatively moving the first and secondsupply members 51, 52 and the substrate P, it is possible to clean, withthe second liquid LQ2, the upper surface (including the circumferentialedge portion), the lower surface, and the side surface of the substrateP. The substrate P may be cleaned by supplying the second liquid LQ2while rotating the substrate P.

The second liquid LQ2, which is adhered to the substrate P, can beremoved by allowing the gas to blow against the substrate P, forexample, from the blow members 37, 38 as shown in FIG. 7 with respect tothe substrate P after the cleaning process. When the substrate P iscleaned, the supply of the second liquid LQ2 and the supply of the gasmay be performed concurrently.

The substrate P can be also cleaned with the second liquid LQ2 suppliedfrom the supply members 51, 52 of the cleaning unit 50 after thesubstrate P, for which the exposure process has been performed, isunloaded out of the substrate holder PH as described above. For example,when the substrate P is subjected to the liquid immersion exposure inthe state in which the substrate P is held by the substrate holder PH,if the liquid makes inflow into the lower surface side of the substrateP via the gap A and the gap B (see FIG. 10), then it is feared that theforeign matter may be adhered to the side surface and the lower surfaceof the substrate P, and the adhesion trace of the first liquid LQ1 maybe formed thereon. In this embodiment, the side surface and the lowersurface of the substrate P can be cleaned satisfactorily as well.Therefore, even when the foreign matter is adhered to the side surfaceand the lower surface of the substrate P, it is possible to decrease orminiaturize or remove the foreign matter. Therefore, it is possible toavoid the pollution of the temperature adjustment mechanism in order toperform the post-baking (PEB) for the substrate P and the transportsystem for the substrate P after the cleaning process. It is alsopossible to avoid the occurrence of the pattern defect by performing thedevelopment process after the cleaning process.

Any liquid, which is different from the first liquid LQ1, can be alsoused as the second liquid LQ2 in the third embodiment. In particular,when only the portion including, for example, the side surface(circumferential edge portion 1As) and the back surface (lower surface)of the substrate P, which does not affect the photosensitive material 2,is cleaned in the third embodiment, an organic solvent such as a thinnercan be used as the second liquid LQ2. Therefore, it is possible toeffectively remove or provide small diameters of the adhered matter(foreign matter) on the side surface and the back surface of thesubstrate P.

Also in the third embodiment, it is possible to use the immersionprocess explained in the first embodiment in combination.

This embodiment is constructed such that the cleaning unit 50 isprovided for the coater/developer apparatus C/D-SYS. It is of courseallowable that the cleaning unit 50 is provided for the exposureapparatus EX-SYS. For example, the cleaning unit 50 may be provided atan intermediate position of the transport passage of the first transportsystem H1 for constructing the exposure apparatus EX-SYS. Accordingly,the substrate P after the liquid immersion exposure process can becleaned with the second liquid LQ2 in the exposure apparatus EX-SYS.Alternatively, the cleaning unit 50 may be provided for the interfaceIF.

The second embodiment and the third embodiment are illustrative of thecase in which the substrate P after the liquid immersion exposure iscleaned. However, an error is caused in some situations such that thesubstrate P, which makes contact with the first liquid LQ1, should beunloaded out of the substrate holder PH before the completion of thedesired process including, for example, the exposure process on thesubstrate stage PST (substrate holder PH). Also in such a situation, itis possible to execute the cleaning process as explained in the secondembodiment and the third embodiment.

A detection unit, which detects the foreign matter (including the liquidand/or the adhesion trace of the liquid) on the surface of the substrateP after the liquid immersion exposure, may be provided. Only when anyunallowable foreign matter is detected on the surface of the substrateP, the substrate P may be cleaned by using the cleaning unit 50. In thesecond and third embodiments, the condition of the cleaning process canbe set on the basis of the information about the substrate P asdescribed above including, for example, the type of the photosensitivematerial 2.

Fourth Embodiment

Next, a fourth embodiment will be explained with reference to FIGS. 17and 18. The feature of the fourth embodiment resides in the fact that athin film 3, which covers the photosensitive material 2, is formed onthe surface of the substrate P to be exposed, as shown in FIG. 17. Thethin film 3 includes, for example, an antireflection film (top ARC) anda top coat film (protective film). In a certain form, the thin film 3 isa top coat film which covers an antireflection film formed on thephotosensitive material 2. The top coat film protects the photosensitivematerial 2 from the liquid, which is formed of, for example, afluorine-based liquid-repellent material.

As schematically shown in FIG. 18, when the thin film 3 is provided, itis possible to suppress the elution of the predetermined substance (forexample, PAG) from the photosensitive material 2 to the liquid, evenwhen the substrate P makes contact with the liquid. Therefore, when thephotosensitive material 2 is coated with the thin film 3, the immersioncondition, which is adopted when the immersion process is performed asexplained in the first embodiment, can be changed with respect to thecase in which the photosensitive material 2 is not coated with the thinfilm 3. That is, it is possible to set the immersion condition for theimmersion process based on the use of the immersion unit 30 and theliquid immersion mechanism 100 depending on the information about thethin film 3 by using the presence or absence of the thin film 3 as theinformation about the substrate P. Specifically, it is possible toappropriately set, for example, the immersion time included in theimmersion condition depending on the presence or absence of the thinfilm 3. For example, when the thin film 3 is present, the predeterminedsubstance is not eluted substantially from the photosensitive material 2to the liquid. Therefore, it is possible to shorten the immersion time,and/or it is possible to omit the immersion process itself.

When the thin film 3 is present, the elution of the predeterminedsubstance from the photosensitive material 2 to the liquid issuppressed. Accordingly, it is possible to suppress the adhesion of theforeign matter to the substrate P and the formation of the adhesiontrace. Therefore, the cleaning condition of the cleaning process asexplained in the second and third embodiments may be appropriately setdepending on the presence or absence of the thin film 3. For example,when the thin film 3 is present, then it is possible to shorten thecleaning time, and/or it is possible to omit the cleaning processitself.

There is also such a possibility that the predetermined substancecontained in the photosensitive material 2 may be eluted into the liquidthrough the thin film 3, and the substance of the material for formingthe thin film 3 may be eluted into the liquid, depending on thesubstance for constructing the thin film 3. Therefore, when theimmersion process and the cleaning process are performed, it isdesirable to consider, for example, the information about the material(substance) of the thin film 3 as well, without being limited to onlythe presence or absence of the thin film 3 on the photosensitivematerial 2, as the information about the substrate P.

When the thin film (top ARC, protective film) 3 is formed on thephotosensitive material 2 in the first embodiment, it is also allowablethat the immersion unit 30 is used as a unit for applying (forming) thethin film 3 as well.

The first and second liquids LQ1, LQ2 may be those which are composed ofthe same material (water) and which have properties or components (waterqualities) different from each other. The items of the property or thecomponent of the liquid herein include, for example, the specificresistance value of the liquid, the total organic carbon (TOC) in theliquid, the foreign matter including particles and bubbles contained inthe liquid, the dissolved gas including the dissolved oxygen (DO) andthe dissolved nitrogen (DN), the metal ion content, the silicaconcentration in the liquid, and the live bacteria or germs. Forexample, the sufficient cleanness is required for the first liquid LQ1to be used for the liquid immersion exposure. However, it is allowablethat the second liquid LQ2, which is used for the immersion process, hasthe cleanness lower than that of the first liquid LQ1. It is alsopossible to use various fluids, for example, the supercritical fluid asthe first and second liquids LQ1, LQ2.

Liquids, which have the same material (water) and which have differenttemperatures, may be used as the first and second liquids LQ1, LQ2.

In the embodiment described above, it is preferable that the cleaningprocess time (Step S7.1) is set so that the period of time, which rangesfrom the completion of the liquid immersion exposure (Step S7) to thestart of the post-baking (Step S8), is within a preset predeterminedperiod of time. If any basic substance such as ammonia exists in theatmosphere in the first chamber apparatus CH1, it is feared that thebasic substance may adhere to the surface of the photosensitive material2, and the basic substance may cause the neutralization reaction withacid to cause the deactivation phenomenon of acid. Therefore, it ispreferable that the post-baking is performed before the neutralizationreaction is accelerated. Therefore, the post-baking can be executedbefore the neutralization reaction is accelerated, by setting thecleaning process time in consideration of the period of time rangingfrom the completion of the liquid immersion exposure to the start of thepost-baking.

In the embodiment described above, the explanation has been made asexemplified by the case in which the chemical amplification type resistis used as the photosensitive material 2 by way of example. However, itis also allowable to use, for example, a novolac resin-based resistcontaining no PAG. Also in this case, the liquid immersion exposureprocess can be performed after removing the foreign matter on thephotosensitive material beforehand by performing the immersion process.It is possible to avoid the formation of the adhesion trace byperforming the cleaning process after the liquid immersion exposureprocess.

In the embodiment described above, the explanation has been made for thecase in which the base material 1 is coated with the photosensitivematerial 2 in order to simplify the explanation. However, even whenpattern layers are already formed on the base material 1 afterperforming several exposure steps, it is possible to perform theimmersion process and the cleaning process as described above. In thiscase, it is also appropriate to consider the elution of the material forforming the pattern layers into the liquid.

As described above, the liquid (first liquid) is pure water in theembodiment of the present invention. Pure water is advantageous in thatpure water is available in a large amount with ease, for example, in thesemiconductor production factory, and pure water exerts no harmfulinfluence, for example, on the optical element (lens) and thephotoresist on the substrate P. Further, pure water exerts no harmfulinfluence on the environment, and the content of impurity is extremelylow. Therefore, it is also expected to obtain the function to clean thesurface of the substrate P and the surface of the optical elementprovided at the end surface of the projection optical system PL. Whenthe purity of pure water supplied from the factory or the like is low,it is also allowable that the exposure apparatus is provided with anultra pure water-producing unit.

It is approved that the refractive index n of pure water (water) withrespect to the exposure light beam EL having a wavelength of about 193nm is approximately 1.44. When the ArF excimer laser beam (wavelength:193 nm) is used as the light source of the exposure light beam EL, thenthe wavelength is shortened on the substrate P by 1/n, i.e., to about134 nm, and a high resolution is obtained. Further, the depth of focusis magnified about n times, i.e., about 1.44 times as compared with thevalue obtained in the air. Therefore, when it is enough to secure anapproximately equivalent depth of focus as compared with the case of theuse in the air, it is possible to further increase the numericalaperture of the projection optical system PL. Also in this viewpoint,the resolution is improved.

When the liquid immersion method is used as described above, thenumerical aperture NA of the projection optical system is 0.9 to 1.3 insome cases. When the numerical aperture NA of the projection opticalsystem is large as described above, it is desirable to use the polarizedillumination, because the image formation performance is deteriorateddue to the polarization effect in some cases with the random polarizedlight which has been hitherto used as the exposure light beam. In thiscase, it is appropriate that the linear polarized illumination, which isadjusted to the longitudinal direction of the line pattern of theline-and-space pattern of the mask (reticle), is effected so that thediffracted light of the S-polarized light component (TE-polarized lightcomponent), i.e., the component in the polarization direction along withthe longitudinal direction of the line pattern is dominantly allowed tooutgo from the pattern of the mask (reticle). When the space between theprojection optical system PL and the resist coated on the surface of thesubstrate P is filled with the liquid, the diffracted light of theS-polarized light component (TE-polarized light component), whichcontributes to the improvement in the contrast, has the hightransmittance on the resist surface, as compared with the case in whichthe space between the projection optical system PL and the resist coatedon the surface of the substrate P is filled with the air (gas).Therefore, it is possible to obtain the high image formation performanceeven when the numerical aperture NA of the projection optical systemexceeds 1.0. Further, it is more effective to appropriately combine, forexample, the phase shift mask and the oblique incidence illuminationmethod (especially the dipole illumination method) adjusted to thelongitudinal direction of the line pattern as disclosed in JapanesePatent Application Laid-open No. 6-188169. In particular, thecombination of the linear polarized illumination method and the dipoleillumination method is effective when the periodic direction of theline-and-space pattern is restricted to one predetermined direction andwhen the hole pattern is clustered in one predetermined direction. Forexample, when a phase shift mask of the half tone type having atransmittance of 6% (pattern having a half pitch of about 45 nm) isilluminated by using the linear polarized illumination method and thedipole illumination method in combination, the depth of focus (DOF) canbe increased by about 150 nm as compared with the use of the randompolarized light provided that the illumination σ, which is prescribed bythe circumscribed circle of the two light fluxes for forming the dipoleon the pupil plane of the illumination system, is 0.95, the radius ofeach of the light fluxes at the pupil plane is 0.125σ, and the numericalaperture of the projection optical system PL is NA=1.2.

It is also effective to adopt a combination of the linear polarizedillumination and the small σ illumination method (illumination methodwherein the σ value, which indicates the ratio between the numericalaperture NAi of the illumination system and the numerical aperture NApof the projection optical system, is not more than 0.4).

For example, when the ArF excimer laser is used as the exposure lightbeam, and the substrate P is exposed with a fine line-and-space pattern(for example, line-and-space of about 25 to 50 nm) by using theprojection optical system PL having a reduction magnification of about¼, then the mask M acts as a polarizing plate due to the Wave guideeffect depending on the structure of the mask M (for example, thepattern fineness and the thickness of chromium), and the diffractedlight of the S-polarized light component (TE-polarized light component)outgoes from the mask M in an amount larger than that of the diffractedlight of the P-polarized light component (TM-polarized light component)which lowers the contrast. In this case, it is desirable to use thelinear polarized illumination as described above. However, even when themask M is illuminated with the random polarized light, it is possible toobtain the high resolution performance even when the numerical apertureNA of the projection optical system PL is large, i.e., 0.9 to 1.3.

When the substrate P is exposed with an extremely fine line-and-spacepattern on the mask M, there is such a possibility that the P-polarizedlight component (TM-polarized light component) is larger than theS-polarized light component (TE-polarized light component) due to theWire Grid effect. However, for example, when the ArF excimer laser isused as the exposure light beam, and the substrate P is exposed with aline-and-space pattern larger than 25 nm by using the projection opticalsystem PL having a reduction magnification of about ¼, then thediffracted light of the S-polarized light component (TE-polarized lightcomponent) outgoes from the mask M in an amount larger than that of thediffracted light of the P-polarized light component (TM-polarized lightcomponent). Therefore, it is possible to obtain the high resolutionperformance even when the numerical aperture NA of the projectionoptical system PL is large, i.e., 0.9 to 1.3.

Further, it is also effective to use the combination of the obliqueincidence illumination method and the polarized illumination method inwhich the linear polarization is effected in the tangential(circumferential) direction of the circle having the center of theoptical axis as disclosed in Japanese Patent Application Laid-open No.6-53120, without being limited to only the linear polarized illumination(S-polarized illumination) adjusted to the longitudinal direction of theline pattern of the mask (reticle). In particular, when the pattern ofthe mask (reticle) includes not only the line pattern extending in onepredetermined direction, but the pattern also includes the line patternsextending in a plurality of different directions in a mixed manner(line-and-space patterns having different periodic directions arepresent in a mixed manner), then it is possible to obtain the high imageformation performance even when the numerical aperture NA of theprojection optical system is large, by using, in combination, the zonalillumination method and the polarized illumination method in which thelight is linearly polarized in the tangential direction of the circlehaving the center of the optical axis, as disclosed in Japanese PatentApplication Laid-open No. 6-53120 as well. For example, when a phaseshift mask of the half tone type having a transmittance of 6% (patternhaving a half pitch of about 63 nm) is illuminated by using, incombination, the zonal illumination method (zonal ratio: ¾) and thepolarized illumination method in which the light is linearly polarizedin the tangential direction of the circle having the center of theoptical axis, the depth of focus (DOF) can be increased by about 250 nmas compared with the use of the random polarized light provided that theillumination σ is 0.95 and the numerical aperture of the projectionoptical system PL is NA=1.00. In the case of a pattern having a halfpitch of about 55 nm and a numerical aperture of the projection opticalsystem NA=1.2, the depth of focus can be increased by about 100 nm.

In addition to the various types of the illumination methods asdescribed above, it is also effective to adapt, for example, theprogressive multi-focal exposure method disclosed in Japanese PatentApplication Laid-open Nos. 4-277612 and 2001-345245, and themultiwavelength exposure method to obtain an effect equivalent to thatof the progressive multi-focal exposure method by using amultiwavelength (for example, biwavelength) exposure light beam.

In the embodiment of the present invention, the optical element LS1 isattached to the end portion of the projection optical system PL. Such anoptical element makes it possible to adjust the optical characteristicsof the projection optical system PL, for example, the aberration (forexample, spherical aberration and coma aberration). The optical element,which is attached to the end portion of the projection optical systemPL, may be an optical plate which is usable to adjust the opticalcharacteristics of the projection optical system PL. Alternatively, theoptical element may be a plane-parallel plate through which the exposurelight beam EL is transmissive.

When the pressure, which is generated by the flow of the liquid LQ, islarge between the substrate P and the optical element disposed at theend portion of the projection optical system PL, it is also allowablethat the optical element is tightly fixed so that the optical element isnot moved by the pressure, without allowing the optical element to beexchangeable.

In the embodiment of the present invention, the space between theprojection optical system PL and the surface of the substrate P isfilled with the liquid. However, for example, it is also allowable thatthe space is filled with the liquid LQ in such a state that a coverglass composed of a parallel flat plate is attached to the surface ofthe substrate P.

In the projection optical system of the embodiment described above, theoptical path space, which is arranged on the image plane side of theoptical element disposed at the end portion, is filled with the liquid.However, as disclosed in International Publication No. 2004/019128, itis also possible to adopt a projection optical system in which theoptical path space arranged on the mask side of the optical elementdisposed at the end portion is also filled with the liquid.

The liquid (first liquid) is water in the embodiment of the presentinvention. However, the liquid may be any liquid other than water. Forexample, when the light source of the exposure light beam EL is the F₂laser, the F₂ laser beam is not transmitted through water. Therefore,those preferably usable as the liquid LQ may include, for example,fluorine-based fluids such as fluorine-based oil and perfluoropolyether(PFPE) through which the F₂ laser beam is transmissive. In this case,the portion, which makes contact with the liquid, is subjected to aliquid-attracting treatment by forming, for example, a thin film with asubstance having a molecular structure containing fluorine having smallpolarity. Alternatively, other than the above, it is also possible touse, as the liquid LQ, those (for example, cedar oil) which have thetransmittance with respect to the exposure light beam EL, which have therefractive index as high as possible, and which are stable against thephotoresist coated on the surface of the substrate P and the projectionoptical system PL. Also in this case, the surface treatment is performeddepending on the polarity of the liquid LQ to be used.

The substrate P, which is usable in the respective embodiments describedabove, is not limited to the semiconductor wafer for producing thesemiconductor device. Those applicable include, for example, the glasssubstrate for the display device, the ceramic wafer for the thin filmmagnetic head, and the master plate (synthetic silica glass, siliconwafer) for the mask or the reticle to be used for the exposureapparatus.

As for the exposure apparatus EX, the present invention is alsoapplicable to the scanning type exposure apparatus (scanning stepper)based on the step-and-scan system for performing the scanning exposurewith the pattern of the mask M by synchronously moving the mask M andthe substrate P as well as the projection exposure apparatus (stepper)based on the step-and-repeat system for performing the full fieldexposure with the pattern of the mask M in a state in which the mask Mand the substrate P are allowed to stand still, while successivelystep-moving the substrate P.

As for the exposure apparatus EX, the present invention is alsoapplicable to the exposure apparatus based on the system in which thefull field exposure is performed on the substrate P by using aprojection optical system (for example, the dioptric type projectionoptical system having a reduction magnification of ⅛ and including nocatoptric element) with a reduction image of a first pattern in a statein which the first pattern and the substrate P are allowed tosubstantially stand still. In this case, the present invention is alsoapplicable to the full field exposure apparatus based on the stitchsystem in which the full field exposure is further performed thereafteron the substrate P by partially overlaying a reduction image of a secondpattern with respect to the first pattern by using the projectionoptical system in a state in which the second pattern and the substrateP are allowed to substantially stand still. As for the exposureapparatus based on the stitch system, the present invention is alsoapplicable to the exposure apparatus based on the step-and-stitch systemin which at least two patterns are partially overlaid and transferred onthe substrate P, and the substrate P is successively moved. Theembodiment described above has been explained as exemplified by theexposure apparatus provided with the projection optical system PL by wayof example. However, the present invention is applicable to the exposureapparatus and the exposure method in which the projection optical systemPL is not used.

The present invention is also applicable to the twin-stage type exposureapparatus. The structure and the exposure operation of the twin-stagetype exposure apparatus are disclosed, for example, in Japanese PatentApplication Laid-open Nos. 10-163099 and 10-214783 (corresponding toU.S. Pat. Nos. 6,341,007, 6,400,441, 6,549,269, and 6,590,634), JapanesePatent Application Laid-open No. 2000-505958 (PCT) (corresponding toU.S. Pat. No. 5,969,441), and U.S. Pat. No. 6,208,407. The disclosuresthereof are incorporated herein by reference within a range ofpermission of the domestic laws and ordinances of the state designatedor selected in this international application.

The present invention is also applicable to an exposure apparatusprovided with a substrate stage which retains the substrate and ameasuring stage which carries various photoelectric sensors andreference members formed with reference marks as disclosed in JapaneseLaid-Open Patent Publication No. 11-135400.

In the embodiment described above, the exposure apparatus, in which thespace between the projection optical system PL and the substrate P islocally filled with the liquid, is adopted. However, the presentinvention is also applicable to a such liquid immersion exposureapparatus that the exposure is performed in a state in which the entiresurface of the substrate as the exposure objective is immersed in aliquid as disclosed, for example, in Japanese Patent ApplicationLaid-open Nos. 6-124873 and 10-303114 and U.S. Pat. No. 5,825,043. Thestructure and the exposure operation of such a liquid immersion exposureapparatus are described in detail, for example, in U.S. Pat. No.5,825,043. The contents of the description in this United States patentdocument are incorporated herein by reference within a range ofpermission of the domestic laws and ordinances of the state designatedor selected in this international application.

As for the type of the exposure apparatus EX, the present invention isnot limited to the exposure apparatus for the semiconductor deviceproduction for exposing the substrate P with the semiconductor devicepattern. The present invention is also widely applicable, for example,to the exposure apparatus for producing the liquid crystal displaydevice or for producing the display as well as the exposure apparatusfor producing, for example, the thin film magnetic head, the imagepickup device (CCD), the reticle, or the mask.

When the linear motor is used for the substrate stage PST and/or themask stage MST, it is allowable to use any one of those of the airfloating type based on the use of the air bearing and those of themagnetic floating type based on the use of the Lorentz's force or thereactance force. Each of the stages PST, MST may be either of the typein which the movement is effected along the guide or of the guidelesstype in which no guide is provided. An example of the use of the linearmotor for the stage is disclosed in U.S. Pat. Nos. 5,623,853 and5,528,118. The contents of the descriptions in the literatures areincorporated herein by reference respectively within a range ofpermission of the domestic laws and ordinances of the state designatedor selected in this international application.

As for the driving mechanism for each of the stages PST, MST, it is alsoallowable to use a plane motor in which a magnet unit provided withtwo-dimensionally arranged magnets and an armature unit provided withtwo-dimensionally arranged coils are opposed to one another, and each ofthe stages PST, MST is driven by means of the electromagnetic force. Inthis arrangement, any one of the magnet unit and the armature unit isconnected to the stage PST, MST, and the other of the magnet unit andthe armature unit is provided on the side of the movable surface of thestage PST, MST.

The reaction force, which is generated in accordance with the movementof the substrate stage PST, may be mechanically released to the floor(ground) by using a frame member so that the reaction force is nottransmitted to the projection optical system PL, as described inJapanese Patent Application Laid-open No. 8-166475 (U.S. Pat. No.5,528,118). The contents of the descriptions in U.S. Pat. No. 5,528,118are incorporated herein by reference within a range of permission of thedomestic laws and ordinances of the state designated or selected in thisinternational application.

The reaction force, which is generated in accordance with the movementof the mask stage MST, may be mechanically released to the floor(ground) by using a frame member so that the reaction force is nottransmitted to the projection optical system PL, as described inJapanese Patent Application Laid-open No. 8-330224 (U.S. Pat. No.5,874,820). The disclosure of U.S. Pat. No. 5,874,820 is incorporatedherein by reference within a range of permission of the domestic lawsand ordinances of the state designated or selected in this internationalapplication.

As described above, the exposure apparatus EX according to theembodiment of the present invention is produced by assembling thevarious subsystems including the respective constitutive elements asdefined in claims so that the predetermined mechanical accuracy, theelectric accuracy, and the optical accuracy are maintained. In order tosecure the various accuracies, those performed before and after theassembling include the adjustment for achieving the optical accuracy forthe various optical systems, the adjustment for achieving the mechanicalaccuracy for the various mechanical systems, and the adjustment forachieving the electric accuracy for the various electric systems. Thesteps of assembling the various subsystems into the exposure apparatusinclude, for example, the mechanical connection, the wiring connectionof the electric circuits, and the piping connection of the air pressurecircuits in correlation with the various subsystems. It goes withoutsaying that the steps of assembling the respective individual subsystemsare performed before performing the steps of assembling the varioussubsystems into the exposure apparatus. When the steps of assembling thevarious subsystems into the exposure apparatus are completed, theoverall adjustment is performed to secure the various accuracies as theentire exposure apparatus. It is desirable that the exposure apparatusis produced in a clean room in which, for example, the temperature andthe cleanness are managed.

As shown in FIG. 19, the microdevice such as the semiconductor device isproduced by performing, for example, a step 201 of designing thefunction and the performance of the microdevice, a step 202 ofmanufacturing a mask (reticle) based on the designing step, a step 203of producing a substrate as a base material for the device, a substrateprocessing step (exposure process step) 204 of exposing a pattern of themask on the substrate by using the exposure apparatus EX of theembodiment described above and developing the exposed substrate, a stepof assembling the device (including machining processes including, forexample, a dicing step, a bonding step, and a packaging step) 205, andan inspection step 206. The substrate processing step 204 includes theimmersion step and the cleaning step as explained with reference toFIGS. 3 and 13 distinctly from the exposure step.

INDUSTRIAL APPLICABILITY

According to the present invention, the substrate can be satisfactorilyprocessed in relation to the liquid immersion exposure. Therefore, it ispossible to produce the device having the desired performance.

1. A substrate processing method comprising: holding a substrate on asubstrate holder; exposing the substrate held on the substrate holder byforming a liquid immersion area of a first liquid on the substrate andradiating an exposure light beam onto the substrate through the firstliquid; immersing the substrate in a second liquid, before the substrateis loaded on the substrate holder and before exposing the substrate; andadjusting a temperature of the substrate to be a predeterminedtemperature after a process of removing the second liquid from thesubstrate and before the substrate is loaded on the substrate holder,wherein the predetermined temperature is based on at least one of thetemperature of the substrate holder and a temperature of the firstliquid.
 2. The substrate processing method according to claim 1,wherein: the substrate includes a base material and a photosensitivematerial with which a surface of the base material is coated; and aliquid immersion condition for immersing the substrate in the secondliquid is set depending on information about the substrate.
 3. Thesubstrate processing method according to claim 2, wherein theinformation about the substrate includes information about thephotosensitive material.
 4. The substrate processing method according toclaim 3, wherein the information about the substrate includes elutiontime for which a part of a substance contained in the photosensitivematerial is eluted into the second liquid.
 5. The substrate processingmethod according to claim 2, wherein the information about the substrateincludes information about a protective film which covers thephotosensitive material therewith.
 6. The substrate processing methodaccording to claim 5, wherein the information about the substrateincludes the presence or absence of the protective film.
 7. Thesubstrate processing method according to claim 2, wherein the liquidimmersion condition includes a removal condition of the second liquid.8. The substrate processing method according to claim 2, wherein theliquid immersion condition for immersing the substrate in the secondliquid includes immersion time.
 9. The substrate processing methodaccording to claim 2, further comprising forming a thin film on thephotosensitive material with which the base material is coated.
 10. Thesubstrate processing method according to claim 1, wherein the liquidimmersion area of the first liquid is formed on the substrate afterremoving the second liquid from the substrate.
 11. The substrateprocessing method according to claim 1, wherein the temperature of thesubstrate is adjusted to compensate a temperature change of thesubstrate caused by heat of vaporization generated when the secondliquid is removed.
 12. The substrate processing method according toclaim 1, wherein the first liquid is the same as the second liquid. 13.The substrate processing method according to claim 1, wherein the firstliquid is different from the second liquid.
 14. The substrate processingmethod according to claim 1, further comprising preparing the substrateby coating a base material with a photosensitive material, andpre-baking the prepared substrate, wherein the substrate is immersed inthe second liquid after pre-baking the substrate.
 15. A method forproducing a device, comprising: the substrate processing method asdefined in claim 14; developing the substrate after exposing thesubstrate; and processing the developed substrate.
 16. The substrateprocessing method according to claim 1, wherein the temperature of thesubstrate is adjusted such that the adjusted temperature isapproximately the same as the temperature of the substrate holder. 17.The substrate processing method according to claim 1, wherein thetemperature of the substrate is adjusted such that the adjustedtemperature is approximately the same as the temperature of the firstliquid.
 18. The substrate processing method according to claim 1,wherein the first liquid and the second liquid are pure water, and thefirst liquid is different from the second liquid in a property or acomponent.
 19. An exposure apparatus which exposes a substrate byforming a liquid immersion area of a first liquid on the substrate andradiating an exposure light beam onto the substrate through the firstliquid, the exposure apparatus comprising: a substrate holder on whichthe substrate is held, the substrate being loaded on the substrateholder after immersing the substrate in a second liquid and after aprocess of removing the second liquid from the substrate; a projectionsystem by which the exposure light beam is radiated onto the substrateheld by the substrate holder through the first liquid in the liquidimmersion area formed on the substrate; and a temperature adjustmentdevice which adjusts a temperature of the substrate to be apredetermined temperature after the process of removing the secondliquid from the substrate and before loading the substrate on thesubstrate holder, wherein the predetermined temperature is based on atleast one of a temperature of the substrate holder and a temperature ofthe first liquid.
 20. The exposure apparatus according to claim 19,further comprising: a transport system which transports the substrate;and an immersion device which is provided at an intermediate position ofa transport passage of the transport system and which immerses thesubstrate in the second liquid before the temperature of the substrateis adjusted by the temperature adjustment device.
 21. The exposureapparatus according to claim 20, wherein the immersion device sets animmersion condition for immersing the substrate in the second liquid onthe basis of information about the substrate.
 22. The exposure apparatusaccording to claim 19, wherein the temperature adjustment device adjuststhe temperature of the substrate to compensate a temperature change ofthe substrate caused by heat of vaporization generated when the secondliquid is removed.
 23. A method for producing a device comprising:exposing a substrate with the exposure apparatus as defined in claim 19;and developing the substrate to form the device.
 24. The exposureapparatus according to claim 19, wherein the first liquid is the same asthe second liquid.
 25. The exposure apparatus according to claim 19,wherein the first liquid and the second liquid are pure water, and thefirst liquid is different from the second liquid in a property or acomponent.
 26. The exposure apparatus according to claim 19, wherein thefirst liquid is different from the second liquid.
 27. The exposureapparatus according to claim 19, wherein the temperature of thesubstrate is adjusted such that the adjusted temperature isapproximately the same as the temperature of the substrate holder. 28.The exposure apparatus according to claim 19, wherein the temperature ofthe substrate is adjusted such that the adjusted temperature isapproximately the same as the temperature of the first liquid.